U.S. patent application number 11/585112 was filed with the patent office on 2007-02-22 for catalyst and process for producing a rigid polyurethane foam.
This patent application is currently assigned to TOSOH CORPORATION. Invention is credited to Hiroyuki Kiso, Yutaka Tamano, Katsumi Tokumoto.
Application Number | 20070043132 11/585112 |
Document ID | / |
Family ID | 29783299 |
Filed Date | 2007-02-22 |
United States Patent
Application |
20070043132 |
Kind Code |
A1 |
Kiso; Hiroyuki ; et
al. |
February 22, 2007 |
Catalyst and process for producing a rigid polyurethane foam
Abstract
An object of the present invention relates to a catalyst for
producing rigid polyurethane foam; wherein the catalyst functions
in a process for producing rigid polyurethane foam having excellent
adhesive strength and flame retardancy. Another object of the
present invention relates to a catalyst for producing rigid
polyisocyanurate foam; wherein the catalyst functions in a process
for producing rigid polyisocyanurate foam having excellent flame
retardancy, adhesive strength, and dimensional stability.
Inventors: |
Kiso; Hiroyuki; (Shunan-shi,
JP) ; Tokumoto; Katsumi; (Shunan-shi, JP) ;
Tamano; Yutaka; (Shunan-shi, JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
TOSOH CORPORATION
4560, Kaisei-cho
Shunan-shi
JP
746-8501
|
Family ID: |
29783299 |
Appl. No.: |
11/585112 |
Filed: |
October 24, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10618693 |
Jul 15, 2003 |
|
|
|
11585112 |
Oct 24, 2006 |
|
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Current U.S.
Class: |
521/131 |
Current CPC
Class: |
C08G 18/18 20130101;
C08G 18/163 20130101; C08G 18/1833 20130101; C08G 18/092 20130101;
C08G 2110/005 20210101; C08G 2110/0025 20210101; C08G 18/1808
20130101; C08G 18/5024 20130101 |
Class at
Publication: |
521/131 |
International
Class: |
C08G 18/48 20060101
C08G018/48 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 15, 2002 |
JP |
2002-205506 |
Aug 26, 2002 |
JP |
2002-245644 |
Sep 6, 2002 |
JP |
2002-261282 |
Apr 15, 2003 |
JP |
2003-110020 |
Claims
1. A process for producing a rigid polyurethane foam, which
comprises reacting a polyol with a polyisocyanate in the presence
of an amine catalyst and a blowing agent, wherein the amine
catalyst is: a catalyst composition comprising an amine compound of
the following formula (1): ##STR16## wherein each of R.sub.1,
R.sub.2 and R.sub.3 which are independent of one another, is a
C.sub.1-20 alkyl group, and at least one compound selected from the
group consisting of triethylenediamine,
N,N,N',N'-tetramethyl-1,6-hexanediamine and
N,N-dimethylcyclohexylamine; and the blowing agent is: at least one
blowing agent selected from the group consisting of
1,1,1,3,3-pentafluoropropane (HFC-245fa),
1,1,1,3,3-pentafluorobutane (HFC-365mfc) and a low boiling point
hydrocarbon.
2. The process for producing a rigid polyurethane foam according to
claim 1, wherein in the formula (1), each of R.sub.1, R.sub.2 and
R.sub.3 which are independent of one another, is a methyl group, an
ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl
group, a heptyl group, an octyl group, a nonyl group, a decyl
group, an undecyl group, a dodecyl group, a tridecyl group, a
tetradecyl group, a heptadecyl group or a hexadecyl group.
3. The process for producing a rigid polyurethane foam according to
claim 1, wherein the amine compound of the formula (1) is at least
one amine compound selected from the group consisting of
trimethylamine, dimethylethylamine, dimethylpropylamine,
dimethylbutylamine, dimethylpentylamine, dimethylhexylamine,
dimethylheptylamine, dimethyloctylamine, dimethylnonylamine,
dimethyldecylamine, dimethylundecylamine, dimethyldodecylamine,
dimethyltridecylamine, dimethyltetradecylamine,
dimethylpentadecylamine and dimethylhexadecylamine.
4. The process for producing a rigid polyurethane foam according to
claim 1, wherein the composition of the amine compound of the
formula (1) and said at least one amine compound selected from the
group consisting of triethylenediamine,
N,N,N',N'-tetramethyl-1,6-hexanediamine and
N,N-dimethylcyclohexylamine, comprises from 10 to 95 wt % of the
amine compound of the formula (1) and from 90 to 5 wt % of said at
least one amine compound selected from the group consisting of
triethylenediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine and
N,N-dimethylcyclohexylamine.
5. The process for producing a rigid polyurethane foam according to
claim 1, wherein the at least one blowing agent comprises said low
boiling point hydrocarbon, which is a hydrocarbon having a boiling
point of from -30 to 90.degree. C.
6. The process for producing a rigid polyurethane foam according to
claim 5, wherein the hydrocarbon having a boiling point of from -30
to 90.degree. C., is at least one hydrocarbon selected from the
group consisting of propane, butane, 2-methylpropane, pentane,
cyclopentane, 2-methylbutane, 2,2-dimethylpropane, cyclopropane,
hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane,
cyclohexane, 2,4-dimethylpropane, 3,3-dimethylpropane and
2,2,3-trimethylbutane.
7. The process for producing a rigid polyurethane foam according to
claim 1, wherein the amine catalyst is used in an amount of from
0.01 to 20 parts by weight per 100 parts by weight of the
polyol.
8. The process for producing a rigid polyurethane foam according to
claim 1, wherein a foam stabilizer is used as an auxiliary
agent.
9. The process for producing a rigid polyurethane foam according to
claim 1, wherein a cross-linking agent and/or a chain extender is
used as an auxiliary agent.
10. The process for producing a rigid polyurethane foam according
to claim 1, wherein a flame retardant is used as an auxiliary
agent.
11. A process for producing a rigid polyisocyanurate foam, which
comprises reacting a polyol with a polyisocyanate in the presence
of a catalyst and a blowing agent, wherein the catalyst is a
catalyst composition comprising an aliphatic amine compound of the
following formula (1): ##STR17## wherein each of R.sub.1, R.sub.2
and R.sub.3 which are independent of one another, is a C.sub.1-20
alkyl group, and a polyisocyanurate catalyst, and the blowing agent
is at least one blowing agent selected from the group consisting of
1,1,1,3,3-pentafluoropropane (HFC-245fa),
1,1,1,3,3-pentafluorobutane (HFC-365mfc) and a low boiling point
hydrocarbon.
12. The process for producing a rigid polyisocyanurate foam
according to claim 11, wherein in the formula (1), each of R.sub.1,
R.sub.2 and R.sub.3 which are independent of one another, is a
methyl group, an ethyl group, a propyl group, a butyl group, a
pentyl group, a hexyl group, a heptyl group, an octyl group, a
nonyl group, a decyl group, an undecyl group, a dodecyl group, a
tridecyl group, a tetradecyl group, a heptadecyl group or a
hexadecyl group.
13. The process for producing a rigid polyisocyanurate foam
according to claim 11, wherein the aliphatic amine compound of the
formula (1) is at least one amine compound selected from the group
consisting of dimethylethylamine, dimethylpropylamine,
dimethylbutylamine, dimethylpentylamine, dimethylhexylamine,
dimethylheptylamine, dimethyloctylamine, dimethylnonylamine,
dimethyldecylamine, dimethylundecylamine, dimethyldodecylaamine,
dimethyltridecylaamine, dimethyltetradecylamine,
dimethylpentadecylamine and dimethylhexadecylamine.
14. The process for producing a rigid polyisocyanurate foam
according to claim 11, wherein the polyisocyanurate catalyst is at
least one polyisocyanurate catalyst selected from the group
consisting of organic metal type catalysts such as alkali metal
salts of carboxylic acids, alkaline earth metal salts of carboxylic
acids, metal alcoholates, metal phenolates and metal hydroxides,
tertiary amines, tertiary phosphines, onium salt compounds of
phosphorus and quaternary ammonium salts.
15. The process for producing a rigid polyisocyanurate foam
according to claim 11, wherein the composition of the aliphatic
amine compound of the formula (1) and the polyisocyanurate
catalyst, comprises from 10 to 90 wt % of the aliphatic amine
compound of the formula (1) and from 90 to 10 wt % of the
polyisocyanurate catalyst.
16. The process for-producing a rigid polyisocyanurate foam
according to claim 11, wherein the catalyst composition comprising
the aliphatic amine of the formula (1) and the polyisocyanurate
catalyst, is used in an amount of from 0.01 to 40 parts by weight
per 100 parts by weight of the polyol.
17. The process for producing a rigid polyisocyanurate foam
according to claim 11, wherein a foam stabilizer is used as an
auxiliary agent.
18. The process for producing a rigid polyisocyanurate foam
according to claim 11, wherein a cross-linking agent and/or a chain
extender is used as an auxiliary agent.
19. The process for producing a rigid polyisocyanurate foam
according to claim 11, wherein a flame retardant is used as an
auxiliary agent
Description
[0001] This is a divisional application of U.S. application Ser.
No. 10/618,693, filed Jul. 15, 2003.
[0002] The present invention relates to a catalyst for producing a
rigid polyurethane foam and a process for producing a rigid
polyurethane foam by means of such a catalyst. In the present
invention, the rigid polyurethane foam includes an isocyanurate
ring-containing polyurethane foam (hereinafter referred to as a
rigid polyisocyanurate foam). More particularly, the present
invention relates to:
[0003] (1) a catalyst for producing a rigid polyurethane foam by
means of at least one blowing agent selected from the group
consisting of 1,1,1,3,3-pentafluoropropane (HFC-245fa),
1,1,1,3,3-pentafluorobutane (HFC-365mfc) and a low boiling point
hydrocarbon, which comprises:
[0004] (A) an aliphatic amine compound and at least one amine
compound selected from the group consisting of triethylenediamine,
N,N,N',N'-tetramethyl-1,6-hexanediamine and
N,N-dimethylcyclohexylamine: or
[0005] (B) an amine compound having an alkyl ether group and/or an
aryl ether group in its molecule;
[0006] (2) a catalyst for producing a rigid polyisocyanurate foam
by means of at least one blowing agent selected from the group
consisting of 1,1,1,3,3-pentafluoropropane (HFC-245fa),
1,1,1,3,3-pentafluorobutane (HFC-365mfc) and a low boiling point
hydrocarbon, which comprises an aliphatic amine compound and a
polyisocyanurate catalyst;
[0007] (3) a process for producing a rigid polyurethane foam
excellent in the adhesive strength and flame retardancy of the
foam, by means of the above-mentioned catalyst for forming a rigid
polyurethane foam and, as a blowing agent, at least one blowing
agent selected from the group consisting of
1,1,1,3,3-pentafluoropropane (HFC-245fa),
1,1,1,3,3-pentafluorobutane (HFC-365mfc) and a low boiling point
hydrocarbon; and
[0008] (4) a process for producing a rigid polyisocyanurate foam
excellent in the flame retardancy, adhesive strength and
dimensional stability of the foam, by means of the above-mentioned
catalyst for producing a rigid polyisocyanurate foam and, as a
blowing agent, at least one blowing agent selected from the group
consisting of 1,1,1,3,3-pentafluoropropane (HFC-245fa),
1,1,1,3,3-pentafluorobutane (HFC-365mfc) and a low boiling point
hydrocarbon.
[0009] Polyurethane foams are widely used as flexible foams to be
used for seat cushions for automobiles, mattresses, furnitures,
etc., as semirigid foams to be used for instrument panels for
automobiles, headrests, armrests, etc., and as rigid foams to be
used for electric refrigerators, building materials, etc.
[0010] The reaction for forming a rigid polyurethane foam consists
mainly of a urethane bond-forming reaction (gelling reaction) by a
reaction of a polyol with an isocyanate, and a urea group-forming
reaction (blowing reaction) by a reaction of an isocyanate with
water. The reaction for forming a rigid polyisocyanurate foam
comprises, in addition to the above two types of reactions, an
isocyanurate ring-forming reaction (trimerization reaction) by
trimerization of an isocyanate. A catalyst presents a substantial
influence not only to the rates of such reactions but also to the
thermal conductivity of the foam, the curing rate of the foam
surface, the adhesive strength, the moldability, the dimensional
stability and the physical properties.
[0011] In recent years, in the production of rigid polyurethane
foams, it is strongly desired to improve the thermal conductivity
from the viewpoint of reduction of costs or energy saving, to
attain an excellent curing rate to improve the productivity, and to
secure excellent moldability to improve the yield.
[0012] Further, dichloromonofluoroethanes (HCFC analogues) which
used to be employed as blowing agents in the production of rigid
polyurethane foams, have an ozone depletion problem. Accordingly,
as substitute blowing agents, in recent years, it has been proposed
to use 1,1,1,3,3-pentafluoropropane (HFC-245fa) or
1,1,1,3,3-pentafluorobutane (HFC-365mfc) as a hydrofluorocarbon
(HFC) free from the ozone depletion problem, or a hydrocarbon such
as 2-methylpropane, pentane, 2-methylbutane or cyclopropane (e.g.
JP-A-2001-158815).
[0013] Further, the flame retardancy, safety, etc. of rigid
polyurethane foams have become important to satisfy Product
Liability (PL) Law, Responsible Care (RC), etc. Among rigid
polyurethane foams, an isocyanurate ring-containing polyurethane
foam is a foam having an isocyanurate structure formed by a
trimerization of an isocyanate and has been widely used as a flame
retardant material, since the decomposition temperature of the
isocyanurate ring is as high as at least 300.degree. C.
[0014] As a catalyst for producing a polyurethane foam, it is
common to employ a catalyst which accelerates the reaction of a
polyisocyanate with a polyol (gelling reaction) and/or the reaction
of a polyisocyanate with water (blowing reaction). Heretofore, an
organic metal catalyst or a tertiary amine catalyst has been used,
and particularly, it is already widely known that a tertiary amine
catalyst will be a catalyst excellent for the production of a
polyurethane foam. Among such tertiary amine catalysts, those
industrially used as catalysts for production of polyurethanes,
may, for example, be compounds such as triethylenediamine,
N,N,N',N'-tetramethyl-1,6-hexanediamine,
N,N-dimethylcyclohexylamine, bis(2-dimethylaminoethyl) ether,
N,N,N',N'',N''-pentamethyldiethylenetriamine, N-methylmorpholine
and N-ethylmorpholine (e.g. JP-A-01-168717, or "Polyurethane Resin
Handbook", edited by Keiji Iwata, published by Nikkan Kogyo
Shinbunsha K.K. in 1987, p. 118).
[0015] On the other hand, as catalysts to accelerate the
polyisocyanurate reaction (trimerization of a polyisocyanate),
heretofore, organic metal type catalysts such as alkali metal salts
of carboxylic acids, alkaline earth metal salts or carboxylic
acids, metal alcoholates, metal phenolates and metal hydroxides,
tertiary amines, tertiary phosphines, onium salt compounds of
phosphorus and quaternary ammonium salts, have been used. Among
such polyisocyanurate catalysts, alkali metal salts of carboxylic
acids, such as potassium acetate and potassium 2-ethylhexanoate,
quaternary ammonium salts such as a hydroxyalkyltrimethyl
quaternary ammonium 2-ethylhexanoate, S-triazine compounds such as
1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, or
specific tertiary amines such as
2,4,6-tris(dimethylaminomethyl)phenol, are industrially widely
used, since their isocyanurate activities are high.
[0016] Further, it is known that a hydroxyalkylquaternary ammonium
compound of the following formula (7) has a high isocyanurate
activities (e.g. JP-A-52-17484): ##STR1## wherein a is 0 or 1; each
of R.sub.1, R.sub.2 and R.sub.3 which are independent of one
another, is a C.sub.1-20 alkyl or hydroxyalkyl group, a C.sub.3-8
cycloalkyl group, an aralkyl group, an aryl group, a C.sub.2-20
alkenyl group, or a C.sub.2-6 alkynyl group, or R.sub.1, R.sub.2
and R.sub.3 together form a heterocyclic structure selected from
the group consisting of triethylenediamine, quinuclidine,
N-methylmorpholine, N-ethylmorpholine and N,N'-dimethylpiperazine;
R.sub.4 is hydrogen, a phenyl group, a C.sub.1-15 alkyl group, a
C.sub.2-15 alkenyl group, a C.sub.1-9 hydroxyalkyl group, a
ketoalkyl group having a total carbon number of from 3 to 15, or an
alkoxyalkyl group having a total carbon number of from 2 to 20; Y
is hydrogen, a C.sub.1-20 alkyl group, a C.sub.2-15 alkenyl group,
a C.sub.3-6 cycloalkyl group, a phenyl group, an alkylphenyl group
having one or more C.sub.1-9 alkyl groups attached to the phenyl
ring, a benzyl group, an alkylbenzyl group having one or more
C.sub.1-9 alkyl groups attached to the ring, or a
CH.sub.(3-b)Z.sub.(b) group (wherein b=1 to 3; Z=OH, CN, Cl, a
C.sub.1-5 alkoxy group, a phenyl or methoxyphenyl group, or a
(CH.sub.2).sub.dCOOR group, wherein d=0 to 4; R=hydrogen or an
alkyl group having at most 20 carbon atoms).
[0017] Further, a process for producing a rigid polyisocyanurate
foam has been proposed wherein a hydroxyalkyl type quaternary
ammonium organic salt such as a quaternary ammonium salt of the
following formula (8), or a quaternary ammonium organic salt of the
following formula (9) is used as a catalyst (e.g. JP-A-10-017638,
JP-A-09-124760): ##STR2## wherein each of A and B which are
independent of each other, is a linear or branched alkylene group
having 2 or 3 carbon atoms, n is an integer of from 1 to 3, each of
R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.4 which are
independent of one another, is a C.sub.1-6 alkyl group, or R.sub.1,
R.sub.2 and R.sub.3, or R.sub.3, R.sub.4 and R.sub.5 may be bonded
to one another to form a heterocyclic structure of a piperazine
ring, R is hydrogen, a phenyl group, a C.sub.1-10 alkyl group, a
C.sub.2-10 alkenyl group or a C.sub.2-10 alkynyl group, and Y-- is
a C.sub.1-20 alkyl or hydroxyalkyl group, a C.sub.2-10 alkenyl
group, a C.sub.3-7 cycloalkyl group, a C.sub.6-24 aryl group, a
C.sub.7-24 aralkyl group, or a carboxylic acid anion having a
methoxybenzyl group; ##STR3## wherein each of R.sub.1 to R.sub.3 is
a C.sub.1-11 linear or branched, saturated or unsaturated
hydrocarbon group, provided that two among R.sub.1 to R.sub.3 may
form a hetero ring via a carbon, oxygen or nitrogen atom, R.sub.4
is a C.sub.1-8 alkyl group or an aromatic hydrocarbon group, and X
is an organic acid group.
[0018] As a catalyst for the production of a polyisocyanurate foam,
it is already known to use in combination a catalyst to accelerate
the reaction of a polyisocyanate with a polyol (gelling reaction)
and/or a catalyst to accelerate the reaction of a polyisocyanate
with water (blowing reaction), and a catalyst to accelerate the
polyisocyanurate reaction (trimerization of a polyisocyanate).
[0019] For example, JP-A-11-140150 discloses, as examples of such a
catalyst, an amine type catalyst such as triethylamine,
N,N-dimethylcyclohexylamine, dimethylpropylamine,
N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropane,
1,3-diamine, N,N,N',N'-tetramethylhexane-1,6-diamine,
pentamethyldiethylenetriamine, tetramethylguanidine or
triethylenediamine; an alcohol amine type catalyst such as
dimethylaminoethanol or dimethylaminoethoxyethanol; an ether amine
type catalyst such as aminopropyl ether, bis(2-dimethylaminoethyl)
ether, ethylene glycol bis(3-diethyl)-aminopropyl ether; an organic
metal catalyst, such as stannous octoate, dibutyltin diacetate,
dibutyltin laurate, dibutyltin mercaptide, dibutyltin dimaleate,
dioctyltin mercaptide, dioctyltin thiocarboxylate, phenylmercury
propionate, an octenate or an organic metal catalyst which can be
represented by the formula R.sub.3Si--SR' or RZn--OR'; a metal
oxide type catalyst such as lithium oxide or tributyltin oxide; a
hydride type catalyst such as sodium borohydride; an alkoxide type
catalyst such as sodium methoxide; a hydroxide type catalyst
containing an element such as quaternary nitrogen or phosphorus;
and a carboxylate type catalyst such as sodium acetate, sodium
carbonate, potassium acetate, nickel naphthenate, cobalt
naphthenate and an alkali soap. It is disclosed that such catalysts
may be used alone or in combination as a mixture.
[0020] Further, as such a catalyst, JP-A-2002-121252 discloses to
use in combination a trimerization catalyst (isocyanurate catalyst)
such as an alkali metal salt of a carboxylic acid such as potassium
octylate, potassium acetate or potassium propionate, a lead
compound such as lead octylate or lead naphthenate, or a s-triazine
compound such as N,N',N''-tris(diaminopropyl)hexahydro-s-triazine,
and a tertiary amine catalyst such as triethylamine,
dimethylethanolamine or pentamethyldiethylenetriamine
(PNMDETA).
[0021] However, HFC-245fa, HFC-365mfc or a hydrocarbon such as
2-methylpropane, pentane, 2-methylbutane or cyclopropane, is hardly
soluble in a polyol as compared with HCFC analogues and is
expensive, and as such, it may be used only in a small amount in an
admixture. Accordingly, in a formulation of a rigid polyurethane
foam using HFC-245fa, HFC-365mfc or a hydrocarbon such as
2-methylpropane, pentane, 2-methylbutane or cyclopropane, as a
blowing agent, if the above-mentioned tertiary amine catalyst is
used, the amount of water to be used will be substantial, whereby
there will be a problem that as compared with a rigid polyurethane
foam using conventional HCFC or the like as a blowing agent, the
foam will be inferior in flowability, adhesive strength and
dimensional stability, and it has been strongly desired to improve
such properties.
[0022] Further, in the process for the production of a rigid
polyisocyanurate foam, in a case where the above-mentioned
conventional polyisocyanurate catalyst, is used alone or in
combination with the above-mentioned catalyst for producing a
polyurethane foam, the urethane and isocyanurate activities are
high at a relatively high temperature, but under a low temperature
reaction condition, such activities are not high enough for curing,
and there has been a problem that brittleness of the surface of the
foam (friability) tends to deteriorate, and the adhesive strength
with a face material will deteriorate, or the flame retardancy will
be substantially poor.
[0023] In a case where a HFC analogue such as HFC-245fa or
HFC-365mfc is used as a blowing agent in the process for producing
a rigid polyisocyanurate foam, as mentioned above, it is hardly
soluble in a polyol and expensive from the viewpoint of the price,
as compared with a HCFC analogue, whereby it may be used only in a
small amount in an-admixture. Accordingly, a formulation is being
studied wherein the amount of the HFC analogue is reduced, and
instead, the amount of water is increased. However, in a case where
the above-mentioned conventional catalyst for producing a
polyurethane foam and polyisocyanurate catalyst are used in
combination, as the amount of water used is increased, the curing
rate, moldability and flowability of the foam will deteriorate, and
brittleness of the surface of the rigid foam (friability) will
increase, whereby the adhesive strength and the dimensional
stability, flame retardancy, etc. will substantially deteriorate.
Therefore, it is strongly desired to develop a catalyst suitable
for a formulation wherein the amount of a HFC analogue is reduced
and the amount of water is increased.
[0024] Further, it is common to add a flame retardant in order to
improve the flame retardancy of a polyurethane foam. However, in
the case of a rigid polyisocyanurate foam, it is important to have
highly thermally stable isocyanurate rings properly formed in the
foam structure in combination with proper use of a flame retardant.
For this purpose, it is strongly desired to develop a catalyst
which has a high polyisocyanurate activity (trimerization activity)
and which is capable of improving the flame retardancy of the
polyisocyanurate foam.
[0025] The present invention has been made in view of the above
problems, and it is an object of the present invention to solve the
problems of the prior art and to provide a process for producing a
rigid polyurethane foam having the flowability, adhesive strength
and dimensional stability of the foam improved in a case where
HFC-245fa, HFC-365mfc or a hydrocarbon is used as a blowing agent,
and a catalyst composition for such a process.
[0026] As a result of an extensive study to solve the above
problems, the present inventors have found a catalyst composition
for producing a rigid polyurethane foam by means of HFC-245fa,
HFC-365mfc or a hydrocarbon as a blowing agent, and have found that
by using the catalyst composition, it is possible to obtain a rigid
polyurethane foam excellent in the flowability, adhesive strength
and dimensional stability of the foam. Further, it has been found
that by using a specific aliphatic amine compound and a
polyisocyanurate catalyst in combination, it is possible to obtain
a rigid polyisocyanurate foam excellent in the curing rate,
adhesive strength, dimensional stability and flame retardancy of
the foam surface. The present invention has been accomplished on
the basis of these discoveries.
[0027] Namely, the present invention provides:
[0028] (1) A catalyst for producing a rigid polyurethane foam by
means of at least one blowing agent selected from the group
consisting of 1,1,1,3,3-pentafluoropropane (HFC-245fa),
1,1,1,3,3-pentafluorobutane (HFC-365mfc) and a low boiling point
hydrocarbon, which comprises:
[0029] (A) an amine compound of the following formula (1): ##STR4##
wherein each of R.sub.1, R.sub.2 and R.sub.3 which are independent
of one another, is a C.sub.1-20 alkyl group, and at least one amine
compound selected from the group consisting of triethylenediamine,
N,N,N',N'-tetramethyl-1,6-hexanediamine and
N,N-dimethylcyclohexylamine; or
[0030] (B) an amine compound having an alkyl ether group and/or an
aryl ether group in its molecule;
[0031] (2) A catalyst for producing a rigid polyisocyanurate foam
by means of at least one blowing agent selected from the group
consisting of 1,1,1,3,3-pentafluoropropane (HFC-245fa),
1,1,1,3,3-pentafluorobutane (HFC-365mfc) and a low boiling point
hydrocarbon, which comprises an aliphatic amine compound of the
following formula (1): ##STR5## wherein each of R.sub.1, R.sub.2
and R.sub.3 which are independent of one another, is a C.sub.1-20
alkyl group, and a polyisocyanurate catalyst;
[0032] (3) A process for producing a rigid polyurethane foam, which
comprises reacting a polyol with a polyisocyanate in the presence
of an amine catalyst and a blowing agent, wherein the amine
catalyst is:
[0033] (A) a catalyst composition comprising an amine compound of
the following formula (1): ##STR6## wherein each of R.sub.1,
R.sub.2 and R.sub.3 which are independent of one another, is a
C.sub.1-20 alkyl group, and at least one compound selected from the
group consisting of triethylenediamine,
N,N,N',N'-tetramethyl-1,6-hexanediamine and
N,N-dimethylcyclohexylamine; or
[0034] (B) a catalyst comprising an amine compound having an alkyl
ether group and/or an aryl ether group in its molecule; and the
blowing agent is:
[0035] at least one blowing agent selected from the group
consisting of 1,1,1,3,3-pentafluoropropane (HFC-245fa),
1,1,1,3,3-pentafluorobutane (HFC-365mfc) and a low boiling point
hydrocarbon; and
[0036] (4) A process for producing a rigid polyisocyanurate foam,
which comprises reacting a polyol with a polyisocyanate in the
presence of a catalyst and a blowing agent, wherein the catalyst is
a catalyst composition comprising an aliphatic amine compound of
the following formula (1): ##STR7## wherein each of R.sub.1,
R.sub.2 and R.sub.3 which are independent of one another, is a
C.sub.1-20 alkyl group, and a polyisocyanurate catalyst, and the
blowing agent is at least one blowing agent selected from the group
consisting of 1,1,1,3,3-pentafluoropropane (HFC-245fa),
,1,1,3,3-pentafluorobutane (HFC-365mfc) and a low boiling point
hydrocarbon.
[0037] Now, the present invention will be described in detail with
reference to the preferred embodiments.
[0038] In the present invention, the rigid urethane foam means a
foam having a highly crosslinked closed cell structure, which is
not reversibly deformable as disclosed by Gunter Oertel,
"Polyurethane Handbook" (1985) Hanser Publishers (Germany), p.
234-313 or by Keiji Iwata "Polyurethane Resin Handbook" (first
edition in 1987) published by Nikkan Kogyo Shinbunsha, p. 224-283.
The physical properties of the rigid urethane foam are not
particularly limited. However, the density is usually 20 within a
range of from 10 to 100 kg/m.sup.3, and the compressive strength is
within a range of from 50 to 1,000 kPa. Further, in the present
invention, the rigid polyurethane foam includes an isocyanurate
ring-containing polyurethane foam (hereinafter referred to as a
rigid polyisocyanurate foam).
[0039] Firstly, the rigid polyurethane foam catalyst of the present
invention will be described.
[0040] The amine catalyst in the present invention is:
[0041] (A) A catalyst composition comprising an amine compound of
the following formula (1): ##STR8## wherein each of R.sub.1,
R.sub.2 and R.sub.3 which are independent of one another, is a
C.sub.1-20 alkyl group, and at least one amine compound selected
from the group consisting of triethylenediamine,
N,N,N',N'-tetramethyl-1,6-hexanediamine and
N,N-dimethylcyclohexylamine; or
[0042] (B) A catalyst comprising an amine compound having an alkyl
ether group and/or an aryl ether group in its molecule.
[0043] In the amine compound of the formula (1) in the present
invention, each of R.sub.1, R.sub.2 and R.sub.3 which are
independent of one another, is preferably a C.sub.1-16 alkyl group,
such as, a methyl group, an ethyl group, a propyl group, a butyl
group, a pentyl group, a hexyl group, a heptyl group, an octyl
group, a nonyl group, a decyl group, an undecyl group, a dodecyl
group, a tridecyl group, a tetradecyl group, a heptadecyl group or
a hexadecyl group.
[0044] In the present invention, the amine compound of the formula
(1) is not particularly limited so long as it corresponds to the
above-described amine compound. Specifically, it may, for example,
be trimethylamine, dimethylethylamine, dimethylpropylamine,
dimethylbutylamine, dimethylpentylamine, dimethylhexylamine,
dimethylheptylamine, dimethyloctylamine, dimethylnonylamine,
dimethyldecylamine, dimethylundecylamine, dimethyldodecylamine,
dimethyltridecylamine, dimethyltetradecylamine,
dimethylpentadecylamine, dimethylhexadecylamine,
dimethylheptadecylamine, dimethyloctadecylamine,
diethylmethylamine, triethylamine, diethylpropylamine,
diethylbutylamine, diethylpentylamine, diethylhexylamine,
diethylheptylamine, diethyloctylamine, diethylnonylamine,
diethyldecylamine, diethylundecylamine, diethyldodecylamine,
diethyltridecylamine, diethyltetradecylamine,
diethylpentadecylamine, diethylhexadecylamine,
diethylheptadecylamine, diethyloctadecylamine,
methylethylpropylamine, methylethylbutylamine,
methylethylpentylamine, methylethylhexylamine,
methylethylheptylamine, methylethyloctylamine,
methylethylnonylamine, methylethyldecylamine,
methylethylundecylamine, methylethyldodecylamine,
methylethyltridecylamine, methylethyltetradecylamine,
methylethylpentadecylamine, methylethylhexadecylamine,
methylethylheptadecylamine or methylethyloctadecylamine.
[0045] Among these aliphatic amine compounds, an aliphatic amine
compound wherein each of R.sub.1 and R.sub.2 is a methyl group, and
R.sub.3 is a C.sub.2-16 alkyl group, is particularly preferred,
since its catalytic activities are high, and it can industrially
advantageously be used. Specifically, dimethylethylamine,
dimethylpropylamine, dimethylbutylamine, dimethylpentylamine,
dimethylhexylamine, dimethylheptylamine, dimethyloctylamine,
dimethylnonylamine, dimethyldecylamine, dimethylundecylamine,
dimethyldodecylamine, dimethyltridecylamine,
dimethyltetradecylamine, dimethylpentadecylamine or
dimethylhexadecylamine may, for example, be mentioned as a
particularly preferred aliphatic amine compound.
[0046] The amine compound of the formula (1) to be used for the
catalyst composition of the present invention, can easily be
produced by a method known in literature. For example, a method by
reductive methylation of a monoamine or amination of an alcohol, or
a method by a reaction of an alkyl halide with a dialkylamine, may
be mentioned. The composition of the amine compound of the above
formula (1) and at least one amine compound selected from the group
consisting of triethylenediamine,
N,N,N',N'-tetramethyl-1,6-hexanediamine and
N,N-dimethylcyclohexylamine, to be used in the present invention,
is not particularly limited, but it preferably comprises from 10 to
95 wt % of the amine compound of the formula (1) and from 90 to 5
wt % of at least one amine compound selected from the group
consisting of triethylenediamine,
N,N,N',N'-tetramethyl-1,6-hexanediamine and
N,N-dimethylcyclohexylamine. If the amine compound of the formula
(1) is less than 10 wt %, the adhesive strength of the foam is
likely to be poor. On the other hand, if the amine compound of the
formula (1) exceeds 95 wt %, the flowability or dimensional
stability of the foam is likely to deteriorate, or the amount of
the catalyst to be used, will increase, and such may be
disadvantageous from the viewpoint of the cost.
[0047] Further, the rigid polyurethane production catalyst of the
present invention which comprises an amine compound having an alkyl
ether group and/or an aryl ether group in its molecule, is not
particularly limited. However, at least one amine compound having
an alkyl ether group and/or an aryl ether group in its molecule,
selected from the group consisting of an amine compound of the
following formula (2): ##STR9## wherein each of R.sub.1 to R.sub.7
which are independent of one another, is hydrogen, a C.sub.1-16
alkyl group, a C.sub.1-16 aryl group, a C.sub.1-6
dimethylaminoalkyl group or a C.sub.1-16 alkoxyalkyl group, A is a
C.sub.1-16 alkyl group or a C.sub.1-16 aryl group, n is an integer
of from 1 to 11, m is an integer of from 1 to 11, a is an integer
of from 0 to 10, b is an integer of from 1 to 10, provided that
R.sub.5 and R.sub.1 or R.sub.2 may bond to form a 5- to 7-membered
ring, and an amine compound of the following formula (3): ##STR10##
wherein R.sub.1, R.sub.6, R.sub.7, A, m and b are as defined in the
above formula (2), may, for example, be mentioned as a preferred
compound.
[0048] Among these, an amine compound of the above formula (2)
wherein each of R.sup.1 to R.sup.7 which are independent of one
another, is a hydrogen atom, a C.sub.1-10 alkyl group, a C.sub.1-10
aryl group, a C.sub.1-6 dimethylaminoalkyl group or a C.sub.1-10
alkoxyalkyl group, n is an integer of from 1 to 11, m is an integer
of from 1 to 11, a is an integer of from 0 to 5, b is an integer of
from 1 to 5, provided that R.sub.5 and R.sub.1 or R.sub.2 may be
bonded to form a 5- to 7-membered ring, or an amine compound of the
above formula (3) wherein each of R.sub.1, R.sub.6 and R.sub.7
which are independent of one another, is a hydrogen atom, a
C.sub.1-10 alkyl group, a C.sub.1-10 aryl group, a C.sub.1-6
dimethylaminoalkyl group or a C.sub.1-10 alkoxyalkyl group, m is an
integer of from 1 to 11, and b is an integer of from 1 to 5, is
preferred as the catalyst for producing a rigid polyurethane foam
of the present invention.
[0049] In the present invention, each of R.sub.1 to R.sub.7 in the
amine compound of the above formula (2), which are independent of
one another, is preferably a hydrogen atom, a methyl group, a
dimethylaminoethyl group, a dimethylaminopropyl group, a
methoxyethyl group, a methoxypropyl group, a methoxyisopropyl
group, an ethoxyethyl group, an ethoxypropyl group, an
ethoxyisopropyl group, a propoxyethyl group, a propoxypropyl group,
a propoxyisopropyl group, a butoxyethyl group, a butoxypropyl group
or a butoxyisopropyl group, provided that R.sub.5 and R.sub.1 or
R.sub.2 may be bonded to form a 5- to 7-membered ring.
[0050] In the present invention, each of R.sub.1, R.sub.6 and
R.sub.7 in the amine compound of the above formula (3), which are
independent of one another, is preferably a hydrogen atom, a methyl
group, a dimethylaminoethyl group, a dimethylaminopropyl group, a
methoxyethyl group, a methoxypropyl group, a methoxyisopropyl
group, an ethoxyethyl group, an ethoxypropyl group, an
ethoxyisopropyl group, a propoxyethyl group, a propoxypropyl group,
a propoxyisopropyl group, a butoxyethyl group, a butoxypropyl group
or a butoxyisopropyl group.
[0051] In the present invention, substituent A in the amine
compound of the above formula (2) or (3) is preferably a methyl
group, an ethyl group, a propyl group, a butyl group, an amyl
group, a hexyl group, a phenyl group or a benzyl group,
particularly preferably a methyl group or an ethyl group, in order
to obtain a rigid polyurethane foam excellent in the adhesive
strength and dimensional stability.
[0052] The amine compound of the above formula (2) wherein R.sub.5
and R.sub.1 or R.sub.2 are bonded to form a 5- to 7-membered ring,
may, for example, be an amine compound of the following formula
(4): ##STR11## wherein R.sub.1, R.sub.6, R.sub.7, A, m and b are as
defined in the above formula (2), an amine compound of the
following formula (5): ##STR12## wherein R.sub.1, R.sub.6, R.sub.7,
A, m and b are as defined in the above formula (2), or an amine
compound of the following formula (6): ##STR13## wherein R.sub.1,
R.sub.6, R.sub.7, A, m and b are as defined in the above formula
(2).
[0053] In the present invention, the catalyst for producing a rigid
polyurethane foam is not particularly limited so long as it
corresponds to the above-mentioned amine compound. Specifically,
the compound of the above formula (1) may, for example, be
N,N-dimethylaminoethyl methyl ether, N,N-dimethylaminoethyl ethyl
ether, N,N-dimethylaminopropyl methyl ether,
N,N-dimethylaminopropyl ethyl ether, N,N-dimethylaminobutyl methyl
ether, N,N-dimethylaminobutyl ethyl ether, N,N-dimethylaminopentyl
methyl ether, N,N-dimethylaminopentyl ethyl ether,
N,N-dimethylaminohexyl methyl ether, N,N-dimethylaminohexyl ethyl
ether, N,N-dimethylaminoheptyl methyl ether,
N,N-dimethylaminoheptyl ethyl ether, N,N-dimethylaminooctyl methyl
ether, N,N-dimethylaminooctyl ethyl ether, N,N-dimethylaminononyl
methyl ether, N,N-dimethylaminononyl ethyl ether,
N,N-dimethylaminodecyl methyl ether, N,N-dimethylaminodecyl ethyl
ether, N,N-dimethylaminoethoxyethyl methyl ether,
N,N-dimethylaminoethoxyethyl ethyl ether,
N,N-dimethylaminoethoxyisopropyl methyl ether,
N,N-dimethylaminoethoxyisopropyl ethyl ether,
N,N-dimethylaminoethoxyethoxyethyl methyl ether,
N,N-dimethylaminoethoxyethoxyethyl ethyl ether,
N,N-dimethylaminoethoxyethoxyisopropyl methyl ether,
N,N-dimethylaminoethoxyethoxyisopropyl ethyl ether,
N,N-dimethylaminoethyl-N'-methylaminoethoxy methyl ether,
N,N-dimethylaminoethyl-N'-methylaminoethoxy ethyl ether,
N,N-dimethylaminoethyl-N'-methylaminoisopropyl methyl ether,
N,N-dimethylaminoethyl-N'-methylaminoisopropyl ethyl ether,
N,N-dimethylaminopropyl-N'-methylaminoethyl methyl ether,
N,N-dimethylaminopropyl-N'-methylaminoethyl ethyl ether,
N,N-dimethylaminopropyl-N'-methylaminoisopropyl methyl ether,
N,N-dimethylaminopropyl-N'-methylaminoisopropyl ethyl ether,
N,N,N'-trimethyl-N'-methoxyethyl bisaminoethyl ether,
N,N,N'-trimethyl-N'-ethoxyethyl bisaminoethyl ether,
N,N,N'-trimethyl-N'-methoxyisopropyl bisaminoethyl ether,
N,N,N'-trimethyl-N'-ethoxyisopropyl bisaminoethyl ether,
N,N-dimethylaminoethyl-N'-methylaminoethyl-N''-methylaminoethyl
methyl ether,
N,N-dimethylaminoethyl-N'-methylaminoethyl-N''-methylaminoethyl
ethyl ether,
N,N-dimethylaminoethyl-N'-methylaminoethyl-N''-methylaminoisopropyl
methyl ether,
N,N-dimethylaminoethyl-N'-methylaminoethyl-N''-methylaminoisopropyl
ethyl ether,
N,N-dimethylaminoethyl-N'-methylaminoethyl-N''-methylaminoethyl-N.-
quadrature.-methylaminoethyl methyl ether,
N,N-dimethylaminoethyl-N'-methylaminoethyl-N''-methylaminoethyl-N.quadrat-
ure.-methylaminoethyl ethyl ether,
N,N-dimethylaminoethyl-N'-methylaminoethyl-N''-methylaminoethyl-N.quadrat-
ure.-methylaminoisopropyl methyl ether,
N,N-dimethylaminoethyl-N'-methylaminoethyl-N''-methylaminoethyl-N.quadrat-
ure.-methylaminoisopropyl ethyl ether,
N,N-bis(3-dimethylaminopropyl)-N-isopropyl methyl ether,
N,N-bis(3-dimethylaminopropyl)-N-isopropyl ethyl ether,
N-(2-methoxyethyl)-N'-methylpiperazine,
N-(2-ethoxyethyl)-N'-methylpiperazine,
5-dimethylamino-3-methyl-1-pentyl methyl ether or
5-dimethylamino-3-methyl-1-pentyl ethyl ether. Further, the amine
compound of the above formula (3) may, for example, be
1-(2'-methoxyethyl)imidazole, 1-(2'-ethoxyethyl)imidazole,
1-(2'-methoxyethyl)-2-methylimidazole,
1-(2'-ethoxyethyl)-2-methylimidazole,
1-(2'-methoxypropyl)-2-methylimidazole or
1-(2'-ethoxypropyl)-2-methylimidazole.
[0054] Among these amine compounds, particularly preferred from the
viewpoint of high catalytic activities are N,N-dimethylaminoethyl
methyl ether, N,N-dimethylaminoethyl ethyl ether,
N,N-dimethylaminopropyl methyl ether, N,N-dimethylaminopropyl ethyl
ether, N,N-dimethylaminobutyl methyl ether, N,N-dimethylaminobutyl
ethyl ether, N,N-dimethylaminopentyl methyl ether,
N,N-dimethylaminopentyl ethyl ether, N,N-dimethylaminohexyl methyl
ether, N,N-dimethylaminohexyl ethyl ether,
N,N-dimethylaminoethoxyethyl methyl ether,
N,N-dimethylaminoethoxyethyl ethyl ether,
N,N-dimethylaminoethyl-N'-methylaminoethyl methyl ether,
N,N-dimethylaminoethyl-N'-methylaminoethyl ethyl ether,
N,N-dimethylaminopropyl-N'-methylaminoethyl methyl ether,
N,N-dimethylaminopropyl-N'-methylaminoethyl ethyl ether,
N,N,N'-trimethyl-N'-methoxyethylbisaminoethyl ether,
N,N,N'-trimethyl-N'-ethoxyethylbisaminoethyl ether,
N,N-dimethylaminoethyl-N'-methylaminoethyl-N''-methylaminoisopropyl
methyl ether,
N,N-dimethylaminoethyl-N'-methylaminoethyl-N''-methylaminoisopropyl
ethyl ether, N,N-bis(3-dimethylaminopropyl)-N-isopropyl methyl
ether, N,N-bis(3-dimethylaminopropyl)-N-isopropyl ethyl ether,
N-(2-methoxyethyl)-N'-methylpiperazine,
N-(2-ethoxyethyl)-N'-methylpiperazine,
5-dimethylamino-3-methyl-1-pentyl methyl ether and
5-dimethylamino-3-methyl-1-pentyl ethyl ether.
[0055] The amine compound of the above formula (1) or (2) to be
used as the catalyst for producing a rigid polyurethane foam of the
present invention, can be easily produced by a method known in
literature. For example, a method by etherification of a
dialkylamino alcohol or by a reaction of an alkyl ether containing
a halogenated group with a dialkylamine, may be mentioned.
[0056] Now, the catalyst for producing a rigid polyisocyanurate
foam of the present invention will be described.
[0057] The catalyst for producing a rigid polyisocyanurate foam of
the present invention comprises an aliphatic amine compound of the
following formula (1): ##STR14## wherein each of R.sub.1, R.sub.2
and R.sub.3 which are independent of one another, is a C.sub.1-20
alkyl group, and a polyisocyanurate catalyst.
[0058] In the aliphatic amine compound of the above formula (1),
each of R.sub.1, R.sub.2 and R.sub.3 which are independent of one
another, is preferably a C.sub.1-16 alkyl group, such as a methyl
group, an ethyl group, a propyl group, a butyl group, a pentyl
group, a hexyl group, a heptyl group, an octyl group, a nonyl
group, a decyl group, an undecyl group, a dodecyl group, a tridecyl
group, a tetradecyl group, a heptadecyl group or a hexadecyl
group.
[0059] The aliphatic amine compound of the above formula (1) is not
particularly limited so long as it corresponds to the
above-mentioned amine compound. Specifically, it may, for example,
be trimethylamine, triethylamine, tributylamine,
dimethylethylamine, dimethylpropylamine, dimethylbutylamine,
dimethylpentylamine, dimethylhexylamine, dimethylheptylamine,
dimethyloctylamine, dimethylnonylamine, dimethyldecylamine,
dimethylundecylamine, dimethyldodecylamine, dimethyltridecylamine,
dimethyltetradecylamine, dimethylpentadecylamine,
dimethylhexadecylamine, dimethylheptadecylamine,
dimethyloctadecylamine, diethylmethylamine, triethylamine,
diethylpropylamine, diethylbutylamine, diethylpentylamine,
diethylhexylamine, diethylheptylamine, diethyloctylamine,
diethylnonylamine, diethyldecylamine, diethylundecylamine,
diethyldodecylamine, diethyltridecylamine, diethyltetradecylamine,
diethylpentadecylamine, diethylhexadecylamine,
diethylheptadecylamine, diethyloctadecylamine,
methylethylpropylamine, methylethylbutylamine,
methylethylpentylamine, methylethylhexylamine,
methylethylheptylamine, methylethyloctylamine,
methylethylnonylamine, methylethyldecylamine,
methylethylundecylamine, methylethyldodecylamine,
methylethyltridecylamine, methylethyltetradecylamine,
methylethylpentadecylamine, methylethylhexadecylamine,
methylethylheptadecylamine or methylethyldiethyloctadecylamine.
[0060] Among these aliphatic amine compounds, particularly
preferred is an aliphatic amine compound wherein each of R.sub.1
and R.sub.2 is a methyl group, and R.sub.3 is a C.sub.2-16 alkyl
group, since its catalytic activities are high, and it can be
industrially advantageously used. Specifically, dimethylethylamine,
dimethylpropylamine, dimethylbutylamine, dimethylpentylamine,
dimethylhexylamine, dimethylheptylamine, dimethyloctylamine,
dimethylnonylamine, dimethyldecylamine, dimethylundecylamine,
dimethyldodecylamine, dimethyltridecylamine,
dimethyltetradecylamine, dimethylpentadecylamine or
dimethylhexadecylamine may, for example, be mentioned as a
particularly preferred aliphatic amine compound.
[0061] As mentioned above, the amine compound of the above formula
(1) to be used for the catalyst composition of the present
invention, can easily be produced by a method known in literature.
Namely, a method by reductive methylation of a monoamine or by
amination of an alcohol, or a method by a reaction of an alkyl
halide with a dialkylamine, may be mentioned.
[0062] The polyisocyanurate catalyst of the present invention is
not particularly limited so long as it is a catalyst to accelerate
the polyisocyanurate reaction (trimerization of a polyisocyanate).
For example, as mentioned above, a conventional organic metal type
catalyst, such as an alkali metal salt of a carboxylic acid, an
alkaline earth metal salt of a carboxylic acid, a metal alcoholate,
a metal phenolate or a metal hydroxide, a tertiary amine, a
tertiary phosphine, an onium salt compound of phosphorus or a
quaternary ammonium salt, may, for example, be used.
[0063] Among them, as an alkali metal salt of a carboxylic acid,
potassium acetate or potassium 2-ethylhexanoate may, for example,
be preferably employed, since the isocyanurate activities are high.
Further, as the tertiary amine, a S-triazine compound such as
1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, or
2,4,6-tris(dimethylaminomethyl)phenol, is preferably employed,
since the catalytic activities and isocyanurate activities are
high, and the total amount of the catalyst to be used, can be
reduced.
[0064] Further, as the quaternary ammonium salt, a
tetraalkylammonium halide such as tetramethylammonium chloride, a
tetraalkylammonium hydroxide such as tetramethylammonium hydroxide,
a hydroxyalkyl quaternary ammonium compound of the above formula
(7) (JP-A-52-17484), a hydroxyalkyl type quaternary ammonium
organic salt such as a quaternary ammonium salt of the above
formula (8) (JP-A-10-017638), a quaternary ammonium organic salt of
the above formula (9) (JP-A-09-124760), a tetraalkylammonium
carbonate such as a quaternary ammonium carbonate of the following
formula (10): ##STR15## wherein each of R.sub.1 to R.sub.8 is a
C.sub.1-12 linear or branched, saturated or unsaturated hydrocarbon
group, n is from 0 to 3, provided that when n=0, any of R.sub.1 to
R.sub.3 may be optionally bonded to R.sub.5 or R.sub.6 to form a
hetero ring, or in a case where n is from 1 to 3, R.sub.5 or
R.sub.6 may be bonded to R.sub.4 to form a hetero ring, (JP-A-1
1-199644), may, for example, be preferably employed, since the
catalytic activities and the isocyanurate activities are high, and
the total amount of the catalyst to be used can be reduced.
[0065] In the present invention, the composition of the aliphatic
amine compound of the above formula (1) and the polyisocyanurate
catalyst, is not particularly limited, but it preferably comprises
from 10 to 90 wt % of the aliphatic amine compound of the formula
(1) and from 90 to 10 wt % ofthe polyisocyanurate catalyst. More
preferably, it comprises from 20 to 90 wt % of the amine compound
and from 80 to 10 wt % of the polyisocyanurate catalyst. If the
polyisocyanurate catalyst exceeds 80 wt %, the adhesive strength of
the foam is likely to deteriorate. On the other hand, if it is less
than 10 wt %, the flame retardancy and dimensional stability of the
foam tends to deteriorate, and the amount of the catalyst to be
used, tends to increase, such being disadvantageous from the
viewpoint of the cost.
[0066] Now, the process for producing a rigid polyurethane foam of
the present invention will be described.
[0067] The catalyst for producing a rigid polyurethane foam of the
present invention is used as an amine catalyst in the process for
producing a rigid polyurethane foam which comprises reacting a
polyol with a polyisocyanate in the presence of an amine catalyst
and a blowing agent.
[0068] In the process of the present invention, in a case where a
catalyst composition comprising the amine compound of the above
formula (1) and at least one member selected from the group
consisting of triethylenediamine,
N,N,N',N'-tetramethyl-1,6-hexanediamine and
N,N-dimethylcyclohexylamine, is used as the amine catalyst, its
amount is usually within a range of from 0.01 to 20 parts by
weight, preferably from 0.05 to 10 parts by weight, per 100 parts
by weight of the polyol to be used. If the amount of the amine
catalyst is less than 0.01 part by weight, the moldability of the
foam tends to deteriorate, and the dimensional stability is likely
to be poor. On the other hand, if the amount of the amine catalyst
exceeds 20 parts by weight, not only the effect corresponding to
the increase of the catalyst can not be obtained, but also the
flowability of the foam is likely to deteriorate.
[0069] Further, in the process of the present invention, in a case
where the catalyst comprising an amine compound having an alkyl
ether group and/or an aryl ether group in its molecule, is used as
the amine catalyst, its amount is usually within a range of from
0.01 to 20 parts by weight, preferably from 0.05 to 10 parts by
weight, per 100 parts by weight of the polyol to be used. If it is
less than 0.01 part by weight, the moldability and adhesive
strength of the foam may deteriorate, and the dimensional stability
may deteriorate. On the other hand, if it exceeds 20 parts by
weight, not only the effect corresponding to the increase of the
catalyst can not be obtained, but also the flowability of the foam
may deteriorate.
[0070] The amine catalyst used for the process for producing a
rigid polyurethane foam of the present invention, is the
above-described catalyst for producing a rigid polyurethane foam of
the present invention. However, in addition, other catalysts may be
used within a range not to depart from the present invention. As
such other catalysts, a conventional organic metal catalyst, a
metal carboxylate, a tertiary amine or a quaternary ammonium salt,
may, for example, be mentioned.
[0071] The organic metal catalyst may be conventional one and is
not particularly limited. For example, stannous diacetate, stannous
dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide,
dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride,
dioctyltin dilaurate, lead octanoate, lead naphthenate, nickel
naphthenate or cobalt naphthenate, may, for example, be
mentioned.
[0072] The metal carboxylate may be conventional one and is not
particularly limited. For example, an alkali metal salt or alkaline
earth metal salt of a carboxylic acid may be mentioned. The
carboxylic acid is not particularly limited, and it may, for
example, be an aliphatic mono- or dicarboxylic acid such as acetic
acid, propionic acid, 2-ethylhexanoic acid or adipic acid, or an
aromatic mono- or dicarboxylic acid such as benzoic acid or
phthalic acid. Further, the metal to form a carboxylate is
preferably an alkali metal such as lithium, sodium or potassium, or
an alkaline earth metal such as calcium or magnesium, as a
preferred example.
[0073] The tertiary amine may be conventional one and is not
particularly limited. For example, it may be a tertiary amine
compound such as N,N,N',N'-tetramethylethylenediamine,
N,N,N',N'-tetramethylpropylenediamine,
N,N,N',N'',N''-pentamethyldiethylenetriamine,
N,N,N',N'',N''-pentamethyl-(3-aminopropyl)ethylenediamine,
N,N,N',N'',N''-pentamethyldipropylenetriamine,
N,N,N',N'-tetramethylguanidine,
1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine,
1,8-diazabicyclo[5.4.0]undecene-7, N,N'-dimethylpiperazine,
N-methylmorpholine, N-ethylmorpholine,
bis(2-dimethylaminoethyl)ether, 1-methylimidazole,
1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole or
1-dimethylaminopropylimidazole.
[0074] The quaternary ammonium salt may be conventional one and is
not particularly limited. For example, it may be a
tetraalkylammonium halide such as tetramethylammonium chloride, a
tetraalkylammonium hydroxide such as tetramethylammonium hydroxide,
or a tetraalkylammonium organic acid salt such as
tetramethylammonium 2-ethylhexanoate,
2-hydroxypropyltrimethylammonium formate or
2-hydroxypropyltrimethylammonium 2-ethylhexanoate.
[0075] As mentioned above, the catalyst for producing a rigid
polyurethane foam of the present invention may be used alone or as
mixed with other catalyst. To prepare a mixture, if necessary, a
solvent such as dipropylene glycol, ethylene glycol, 1,4-butanediol
or water may be used. The amount of the solvent is not limited, but
preferably at most 3 times by weight the total amount of the
catalyst. If it exceeds 3 times by weight, the physical properties
of the foam may be influenced, and such is not desirable also from
the economical reason. In the-present invention, the catalyst thus
formulated may be added to a polyol, or various amine. catalysts
may be separately added to a polyol. Thus, the manner of its use is
not particularly limited.
[0076] The polyol to be used in the present invention may, for
example, be a conventional polyether polyol, polyester polyol or
polymer polyol, and it may further be a flame retardant polyol such
as a phosphorus-containing polyol or a halogen-containing polyol.
These polyols may be used alone or in combination as a mixture, as
the case requires.
[0077] The polyether polyol to be used in the process of the
present invention may, for example, be one produced by a method
disclosed e.g. by Gunter Oertel, "Polyurethane Handbook" (1985)
Hanser Publishers (Germany), p. 42-53 by using as a starting
material a compound having at least two active hydrogen groups,
such as a polyhydric alcohol such as ethylene glycol, propylene
glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol or
sucrose, an amine such as ethylenediamine, an aromatic amine
compound such as toluenediamine or diphenylmethane-4,4-diamine, or
an alkanolamine such as ethanolamine or diethanolamine, and by
subjecting such a starting material to addition reaction with an
alkylene oxide such as ethylene oxide or propylene oxide.
[0078] The polyester polyol to be used in the process of the
present invention may, for example, be one obtained from a reaction
of a dibasic acid with glycol, a polyester polyol obtained from a
DMT residue or phthalic anhydride as the starting material, or a
polyester polyol led by a waste from the production of nylon, a
waste of pentaerythritol or trimethylolpropane, a waste of a
phthalic acid type polyester, or derivatives from these waste
products, as disclosed by Keiji Iwata "Polyurethane Resin Handbook"
(first edition in 1987), Nikkan Kogyo Shinbunsha, p. 116-p.
117.
[0079] The polymer polyol to be used in the process of the present
invention may, for example, be a polymer polyol obtained by
reacting the above-mentioned polyether polyol with an ethylenically
unsaturated monomer such as butadiene, acrylonitrile or styrene in
the presence of a radical polymerization catalyst.
[0080] The flame retardant polyol to be used in the process of the
present invention may, for example, be a phosphorus-containing
polyol obtained by adding an alkylene oxide to a phosphoric acid
compound, a halogen-containing polyol obtained by ring opening
polymerization of epichlorohydrin or trichlorobutylene oxide, or
phenol polyol.
[0081] In the process of the present invention, a polyol having an
average hydroxyl value of from 100 to 800 mgKOH/g is preferred, and
a polyol having an average hydroxyl value of from 200 to 700
mgKOH/g is particularly preferred.
[0082] The polyisocyanate to be used in the present invention may
be conventional one and is not particularly limited. For example,
it may be an aromatic polyisocyanate such as toluene diisocyanate
(TDI), diphenylmethane diisocyanate (MDI), naphthylene diisocyanate
or xylylene diisocyanate, an aliphatic polyisocyanate such as
hexamethylene diisocyanate, an alicyclic polyisocyanate such as
dicyclohexyl diisocyanate or isophorone diisocyanate, or a mixture
thereof. Among these, preferred is TDI or its derivative, or MDI or
its derivative, and they may be used in combination as a
mixture.
[0083] TDI and its derivative may, for example, be a mixture of
2,4-TDI and 2,6-TDI, or a terminal isocyanate prepolymer derivative
of TDI. MDI or its derivative may, for example, be a mixture of MDI
and its polymer polyphenylpolymethylene diisocyanate, and/or a
diphenylmethane diisocyanate derivative having a terminal
isocyanate group.
[0084] The mixing ratio of the polyisocyanate and the polyol is not
particularly limited, but as represented by the isocyanate index
(isocyanate groups/active hydrogen groups reactive with isocyanate
groups), it is usually preferably within a range of from 60 to
400.
[0085] The blowing agent to be used in the process of the present
invention is at least one blowing agent selected from the group
consisting of 1,1,1,3,3-pentafluoropropane (HFC-245fa),
1,1,1,3,3-pentafluorobutane (HFC-365mfc) and a low boiling point
hydrocarbon.
[0086] In the present invention, the low boiling point hydrocarbon
means a hydrocarbon having a boiling point of from -30 to
90.degree. C. Among such, preferred is propane, butane,
2-methylpropane, pentane, cyclopentane, 2-methylbutane,
2,2-dimethylpropane, cylopropane, hexane, 2-methylpentane,
3-methylpentane, 2,2-dimethylbutane, cyclohexane,
2,4-dimethylpropane, 3,3-dimethylpropane or 2,2,3-trimethylbutane,
since it is inexpensive from the viewpoint of the price or since it
is easy to handle. More preferred is propane, butane, pentane,
cyclopentane or hexane, which is a hydrocarbon having a boiling
point of from -30 to 70.degree. C.
[0087] In the process of the present invention, as the blowing
agent, it is possible to further use water or a flon compound other
than 1,1,1,3,3-pentafluoropropane (HFC-245fa) or
1,1,1,3,3-pentafluorobutane (HFC-365mfc).
[0088] Such a flon compound may, for example, be a HCFC analogue
such as 1,1-dichloro-1-fluoroethane (HCFC-141b),
1-chloro-1,1-difluoroethane (HCFC-142b) or chlorodifluoromethane
(HCFC-22), a HFC-134 analogue such as 1,1,1,2-tetrafluoroethane
(HFC-134a), a HFC-227 analogue such as
1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), or a HFE analogue
such as 1,1,1-trifluoroethyldifluoromethyl ether (HFE-245mf),
1,1,2,2-tetrafluoroethyl methyl ether (HFE-254pc) or
1,1,2,2-tetrafluoroethyl-1,1,1-trifluoroethyl ether
(HFE-347pc-f).
[0089] In the process of the present invention, a specific
combination of blowing agents may, for example, be a mixture of
HFC-245fa and water and/or a low boiling point hydrocarbon, a
mixture of HFC-365mfc and water and/or a low boiling point
hydrocarbon, a mixture of HFC-245fa, HFC-365mfc and water and/or a
low boiling point hydrocarbon, or a mixture of water and a low
boiling point hydrocarbon.
[0090] In the process of the present invention, the amount of the
blowing agent is determined depending upon the desired density and
physical properties of the foam and is not particularly limited.
Specifically, however, it is selected so that the density of the
obtained foam will usually be from 10 to 200 kg/m.sup.3, preferably
from 20 to 100 kg/m.sup.3. The amount of water is not particularly
limited, but it is usually from 0.1 to 10 parts by weight,
preferably from 0.5 to 5 parts by weight, per 100 parts by weight
of the polyol. If the amount of water is less than 0.1 part by
weight, the amount of at least one blowing agent selected from the
group consisting of 1,1,1,3,3-pentafluoropropane (HFC-245fa),
1,1,1,3,3-pentafluorobutane (HFC-365mfc) and a low boiling point
hydrocarbon, will increase, such being disadvantageous from the
viewpoint of the cost. On the other hand, if the amount of water
exceeds 10 parts by weight, the curing speed of the foam tends to
be slow, and the friability of the foam surface tends to be large,
whereby the adhesion with a face material is likely to be
substantially poor.
[0091] In the process of the present invention, the polyol and the
polyisocyanate may be reacted in the presence of the amine
catalyst, the blowing agent and an auxiliary agent, as the case
requires. Such an auxiliary agent may, for example, be a foam
stabilizer, a crosslinking agent and/or a chain extender, or a
flame retardant.
[0092] In the process of the present invention, as the foam
stabilizer, a surfactant may be employed. As a useful surfactant, a
conventional organic silicone type surfactant may, for example, be
mentioned. Specifically, a nonionic surfactant such as an organic
siloxane/polyoxyalkylene copolymer or a silicone/grease copolymer,
or a mixture thereof, may, for example, be mentioned. The amount of
such a foam stabilizer is usually from 0.1 to, 10 parts by weight
per 100 parts by weight of the polyol.
[0093] In the present invention, the crosslinking agent or the
chain extender may, for example, be a polyhydric alcohol such as
ethylene glycol, 1,4-butanediol or glycerol, an amine polyol having
a low molecular weight such as diethanolamine or triethanolamine,
or a polyamine such as ethylenediamine, xylylenediamine or
methylenebisorthochloroaniline.
[0094] In the process of the present invention,.the flame retardant
may, for example, be a reactive flame retardant like a
phosphorus-containing polyol such as propoxylated phosphoric acid
or propoxylated dibutylpyrophosphoric acid obtainable by an
addition reaction of phosphoric acid with an alkylene oxide, a
tertiary phosphoric acid ester such as tricresyl phosphate, a
halogen-containing tertiary phosphoric acid ester such as
tris(2-chloroethyl) phosphate or tris(chloropropyl) phosphate, a
halogen-containing organic compound such as dibromopropanol,
dibromoneopentyl glycol or tetrabromobisphenol A, or an inorganic
compound such as antimony oxide, magnesium carbonate, calcium
carbonate or aluminum phosphate. The amount of the flame retardant
is not particularly limited, since it varies depending upon the
required flame retardancy, but it is usually from 4 to 20 parts by
weight, per 100 parts by weight of the polyol.
[0095] In the present invention, a colorant, an age-preventing
agent and other conventional known additives may further be used,
as the case requires. The types and amounts of such additives may
be within the usual ranges of the additives to be used.
[0096] The process of the present invention is carried out by
rapidly mixing and stirring a mixed solution obtained by mixing the
above-mentioned starting materials (the polyol, the polyisocyanate,
the amine catalyst, the blowing agent, the auxiliary agent, the
additives, etc.), and then injecting it into a suitable container
or mold, followed by foam molding. The mixing and stirring may be
carried out by using a common stirrer or dedicated polyurethane
foaming machine. As the polyurethane foaming machine, high
pressure, low pressure and spray type machines can be used.
[0097] The product produced by the process of the present invention
may be used for various applications. For example, it may be
applied to a freezer, a refrigerator, a heat shielding building
material, etc.
[0098] Now, among processes for forming rigid polyurethane foams of
the present invention, a process for forming a rigid
polyisocyanurate foam will be described.
[0099] The catalyst for producing a rigid polyisocyanurate foam of
the present invention is used as a catalyst when a rigid
polyisocyanurate foam is produced by reacting a polyol with a
polyisocyanate in the presence of a catalyst and a blowing
agent.
[0100] In the process for producing a rigid polyisocyanurate foam
of the present invention, the amount of the catalyst composition
for producing a rigid polyisocyanurate foam, which comprises an
aliphatic amine compound of the above formula (1) and a
polyisocyanurate catalyst, is usually within a range of from 0.01
to 40 parts by weight, preferably from 0.1 to 20 parts by weight,
per 100 parts by weight of the polyol to be used. If the amount is
less than 0.01 part by weight, the moldability of the foam tends to
deteriorate, and the dimensional stability is likely to be poor. On
the other hand, if it exceeds 40 parts by weight, not only the
effect of increasing the catalyst can not be obtained, but the
flowability of the foam is likely to deteriorate.
[0101] The catalyst to be used in the process for producing a rigid
polyisocyanurate foam of the present invention, is the
above-mentioned catalyst for producing a rigid polyisocyanurate
foam of the present invention. However, other catalysts may further
be used in combination within a range not to depart from the
present invention. As such other catalysts, a known tertiary amine
or organic metal compound may, for example, be mentioned.
[0102] The tertiary amine may be conventional one and is not
particularly limited. It may, for example, be
N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetra
methylpropylenediamine,
N,N,N',N'',N''-pentamethyldiethylenetriamine,
N,N,N',N'',N''-pentamethyl-(3-aminopropyl)ethylenediamine,
N,N,N',N'',N''-pentamethyldipropylenetriamine,
N,N,N',N'-tetramethylguanidine,
1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine,
1,8-diazabicyclo[5.4.0]undecene-7, N,N'-dimethylpiperazine,
N-methylmorpholine, N-ethylmorpholine,
bis(2-dimethylaminoethyl)ether, 1-methylimidazole,
1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole or
1-dimethylaminopropylimidazole.
[0103] Further, the organic metal compound may be conventional one
and is not particularly limited. It may, for example, be stannous
diacetate, stannous dioctoate, stannous dioleate, stannous
dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin
dilaurate, dibutyltin dichloride, dioctyltin dilaurate, lead
octylate, lead naphthenate, nickel naphthenate, cobalt naphthenate,
or lithium, sodium or potassium carboxylate.
[0104] The catalyst composition comprising the aliphatic amine
compound of the above formula (1) and the polyisocyanurate
catalyst, of the present invention, may be used alone or as mixed
with other catalysts, as mentioned above. To prepare a mixture, a
solvent such as dipropylene glycol, ethylene glycol, 1,4-butanediol
or water may be used, as the case requires. The amount of the
solvent is not particularly limited, but it is preferably at most 3
times by weight to the total amount of the catalyst. If it exceeds
3 times by weight, the physical properties of the foam will be
influenced, and such is undesirable also for an economical reason.
The catalyst thus formulated, may be used by adding it to the
polyol, or various amine catalysts may separately be added to the
polyol. Thus, the manner of its use is not particularly
limited.
[0105] The polyol to be used in the process of the present
invention may, for example, be a conventional polyether polyol,
polyester polyol or polymer polyol, and it may further be a flame
retardant polyol such as a phosphorus-containing polyol or a
halogen-containing polyol, or a phenol type polyol such as a
Mannich base polyol. These polyols may be used alone or in
combination as a mixture, as the case requires.
[0106] The polyether polyol may, for example, be one produced by a
method disclosed, for example, by Gunter Oertel, "Polyurethane
Handbook" (1985) Hanser Publishers (Germany), p. 42-53 by using as
a starting material a compound having at least two active hydrogen
groups, such as a polyhydric alcohol such as ethylene glycol,
propylene glycol, glycerol, trimethylolpropane or pentaerythritol,
an aliphatic amine such as ethylenediamine, an aromatic amine such
as toluenediamine, an alkanolamine such as ethanolamine or
diethanolamine, sorbitol or sucrose and by subjecting such a
starting material to addition reaction with an alkylene oxide such
as ethylene oxide or propylene oxide.
[0107] The polyester polyol to be used in the process of the
present invention may, for example, be one obtained from a reaction
of a dibasic acid with glycol, a polyester polyol obtained from a
DMT residue or phthalic anhydride as the starting material, or a
polyester polyol led by a waste from the production of nylon, a
waste of pentaerythritol or trimethylolpropane, a waste of a
phthalic acid type polyester, or derivatives from these waste
products, as disclosed by Keiji Iwata "Polyurethane Resin Handbook"
(first edition in 1987), Nikkan Kogyo Shinbunsha, p. 116-p.
117.
[0108] The polymer polyol may, for example, be a polymer polyol
obtained by reacting the above-mentioned polyether polyol with an
ethylenically unsaturated monomer such as butadiene, acrylonitrile
or styrene in the presence of a radical polymerization
catalyst.
[0109] The flame retardant polyol may, for example, be a
phosphorus-containing polyol obtained by adding an alkylene oxide
to a phosphoric acid compound, a halogen-containing polyol obtained
by ring opening polymerization of epichlorohydrin or
trichlorobutylene oxide, or phenol polyol such as Mannich base
polyol.
[0110] Such a polyol is preferably a polyol having an average
hydroxyl value of from 50 to 1,000 mgKOH/g, particularly preferably
a polyol having an average hydroxyl value of from 100 to 800
mgKOH/g.
[0111] The polyisocyanate to be used in the present invention may
be conventional one and is not particularly limited. It may, for
example, be an aromatic polyisocyanate such as toluene diisocyanate
(TDI), diphenylmethane diisocyanate (MDI), naphthylene diisocyanate
or xylylene diisocyanate, an aliphatic polyisocyanate such as
hexamethylene diisocyanate, an alicyclic polyisocyanate such as
dicyclohexyl diisocyanate or isophorone diisocyanate, or a mixture
thereof.
[0112] Among these, preferred is TDI or its derivative, or MDI or
its derivative, and they may be used in combination as a
mixture.
[0113] TDI and its derivative may, for example, be a mixture of
2,4-TDI and 2,6-TDI, or a terminal isocyanate prepolymer derivative
of TDI. MDI or its derivative may, for example, be a mixture of MDI
and its polymer polyphenylpolymethylene diisocyanate, and/or a
diphenylmethane diisocyanate derivative having a terminal
isocyanate group.
[0114] The mixing ratio of the polyisocyanate and the polyol is not
particularly limited, but as represented by the isocyanate index
(isocyanate groups/active hydrogen groups reactive with isocyanate
groups), it is usually preferably within a range of from 110 to
400.
[0115] The blowing agent to be used in the process of the present
invention is at least one blowing agent selected from the group
consisting of 1,1,1,3,3-pentafluoropropane (HFC-245fa),
1,1,1,3,3-pentafluorobutane (HFC-365mfc) and a low boiling point
hydrocarbon.
[0116] In the present invention, the low boiling point hydrocarbon
means a hydrocarbon having a boiling point of from -30 to
90.degree. C. Among such, preferred is propane, butane,
2-methylpropane, pentane, cyclopentane, 2-methylbutane,
2,2-dimethylpropane, cylopropane, hexane, 2-methylpentane,
3-methylpentane, 2,2-dimethylbutane, cyclohexane,
2,4-dimethylpropane, 3,3-dimethylpropane or 2,2,3-trimethylbutane,
since it is inexpensive from the viewpoint of the price or since it
is easy to handle. More preferred is propane, butane, pentane,
cyclopentane or hexane.
[0117] In the process of the present invention, as the blowing
agent, water or a flon compound other than
1,1,1,3,3-pentafluoropropane (HFC-245fa) or
1,1,1,3,3-pentafluorobutane (HFC-365mfc), may further be used.
[0118] Such a flon compound may, for example, be a HCFC analogue
such as 1,1-dichloro-1-fluoroethane (HCFC-141b),
1-chloro-1,1-difluoroethane (HCFC-1 42b) or chlorodifluoromethane
(HCFC-22), a HFC-134 analogue such as 1,1,1,2-tetrafluoroethane
(HFC-134a), a HFC-227 analogue such as
1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), or a HFE analogue
such as 1,1,1-trifluoroethyldifluoromethyl ether (HFE-245mf),
1,1,2,2-tetrafluoroethyl methyl ether (HFE-254pc) or
1,1,2,2-tetrafluoroethyl-1,1,1-trifluoroethyl ether
(HFE-347pc-f).
[0119] In the process of the present invention, a specific
combination of blowing agents may, for example, be a mixture of
HFC-245fa and water and/or a low boiling point hydrocarbon, a
mixture of HFC-365mfc and water and/or a low boiling point
hydrocarbon, a mixture of HFC-245fa, HFC-365mfc and water and/or a
low boiling point hydrocarbon, or a mixture of water and a low
boiling point hydrocarbon.
[0120] In the process of the present invention, the amount of the
blowing agent is determined depending upon the desired density and
physical properties of the foam and is not particularly limited.
Specifically, however, it is selected so that the density of the
obtained foam will usually be from 10 to 200 kg/m.sup.3, preferably
from 20 to 100 kg/m.sup.3. The amount of water is not particularly
limited, but it is usually from 0.1 to 10 parts by weight,
preferably from 0.5 to 5 parts by weight, per 100 parts by weight
of the polyol. If the amount of water is less than 0.1 part by
weight, the amount of at least one blowing agent selected from the
group consisting of 1,1,1,3,3-pentafluoropropane (HFC-245fa),
1,1,1,3,3-pentafluorobutane (HFC-365mfc) and a low boiling point
hydrocarbon, will increase, such being disadvantageous from the
viewpoint of the cost.
[0121] In the process for producing a rigid polyisocyanurate foam
of the present invention, an auxiliary agent other than the above
may be used, as the case requires. Such an auxiliary agent may, for
example, be a foam stabilizer, a crosslinking agent or a chain
extender, or a flame retardant.
[0122] In the present invention, if required, as a foam stabilizer,
a surfactant may be used. A useful surfactant may for example, be a
conventional organic silicone type surfactant. Specifically, it
may, for example, be a nonionic surfactant such as an organic
siloxane/polyoxyalkylene copolymer or a silicone/grease copolymer,
or a mixture thereof. The amount of such a foam stabilizer is
usually from 0.1 to 10 parts by weight per 100 parts by weight of
the polyol.
[0123] In the present invention, the crosslinking agent or the
chain extender may, for example, be a polyhydric alcohol such as
ethylene glycol, 1,4-butanediol or glycerol, an amine polyol having
a low molecular weight such as diethanolamine or triethanolamine,
or a polyamine such as ethylenediamine, xylylenediamine or
methylenebisorthochloroaniline.
[0124] In the process of the present invention, a flame retardant
may be employed as the case requires. A useful flame retardant may,
for example, be a reactive flame retardant like a
phosphorus-containing polyol such as a propoxylated phosphoric acid
or a propoxylated dibutylpyrophosphoric acid, obtained by an
addition reaction of phosphoric acid with an alkylene oxide, a
tertiary phosphoric acid ester such as tricresyl phosphate, a
halogen-containing tertiary phosphoric acid ester such as
tris(2-chloroethyl) phosphate or tris(chloropropyl) phosphate, a
halogen-containing organic compound such as dibromopropanol,
dibromoneopentyl glycol or tetrabromobisphenol A, or an inorganic
compound such as antimony oxide, magnesium carbonate, calcium
carbonate or aluminum phosphate. Its amount is not particularly
limited and varies depending upon the required flame retardancy,
but it is usually from 4 to 20 parts by weight, per 100 parts by
weight of the polyol.
[0125] In the present invention, a colorant, an age-preventing
agent and other conventional known additives may further be used,
as the case requires. The types and amounts of such additives may
be within the usual ranges of the additives to be used.
[0126] The process of the present invention is carried out by
rapidly mixing and stirring a mixed solution obtained by mixing the
above-mentioned starting materials and then injecting it into a
suitable container or mold, followed by foam molding. The mixing
and stirring may be carried out by using a common stirrer or
dedicated polyurethane foaming machine. As the polyurethane foaming
machine, high pressure, low pressure and spray type machines can be
used.
[0127] The product produced by the process of the present invention
may be used for various applications. For example, it may be
applied to a freezer, a refrigerator, a heat shielding building
material, etc.
[0128] According to the process of the present invention, even if
at least one blowing agent selected from the group consisting of
1,1,1,3,3-pentafluoropropane (HFC-245fa),
1,1,1,3,3-pentafluorobutane (HFC-365mfc) and a low boiling point
hydrocarbon, is used as a blowing agent, it is possible to produce
a rigid polyurethane foam excellent in the flowability, adhesive
strength and dimensional stability of the foam, without impairing
the physical properties of the foam. Further, according to the
process of the present invention, it is possible to obtain a rigid
polyurethane foam having physical properties comparable to a foam
produced by means of a conventional blowing agent (HCFC-14 1b).
[0129] Further, according to the process of the present invention,
even if at least one blowing agent selected from the group
consisting of 1,1,1,3,3-pentafluoropropane (HFC-245fa),
1,1,1,3,3-pentafluorobutane (HFC-365mfc) and a low boiling point
hydrocarbon, is used as a blowing agent, it is possible to produce
a rigid polyisocyanurate foam excellent in the flame retardancy,
adhesive strength and dimensional stability of the foam, without
impairing the physical properties of the foam. Further, according
to the process of the present invention, it is possible to obtain a
rigid polyisocyanurate foam having physical properties comparable
to a foam produced by a conventional process.
[0130] Now, with reference to Examples and Comparative Examples,
the catalyst for producing a rigid polyurethane foam and the
process for producing a rigid polyurethane foam by means of such a
catalyst, will be described. However, it should be understood that
the present invention is no by means restricted by such specific
Examples.
[0131] In the following Examples and Comparative Examples, the
various properties were measured by the following measuring
methods.
[0132] Measured Items for the Reactivity
[0133] Cream time: The time until the foam starts to rise was
measured by visual observation.
[0134] Gel time: As the reaction proceeds, the time until the
liquid substance changes to a resinous substance, was measured.
[0135] Tack free time: The time until tackiness of the foam surface
disappears, was measured.
[0136] Rise time: The time until the rise of the foam stops, was
measured by visual observation.
[0137] Flowability of foam: A predetermined amount of a mixed
liquid was injected into an aluminum mold of 100.times.25.times.3.0
cm, and the length (cm) of the formed foam was measured. The longer
the length of the foam, the better the flowability.
[0138] Core Density of Foam:
[0139] Free foaming was carried out by means of an aluminum mold of
50.times.50.times.4.5 cm, and the center portion of the formed foam
was cut into a size of 20.times.20.times.3 cm, whereupon the size
and weight were accurately measured, and core density was
calculated.
[0140] Adhesive Strength of Foam:
[0141] Forming was carried out by setting a zinc-lined iron plate
of 5.times.5 cm on the upper side of an aluminum mold of
25.times.25.times.8.0 cm. After foaming for 1 hour, the peel
strength at 90.degree. of the set iron plate was measured and taken
as the adhesive strength of the foam.
[0142] Dimensional Stability of Foam:
[0143] A foam foamed in an aluminum mold of 50.times.50.times.4.5
cm was maintained under a condition of -30.degree. C..times.48
hours, whereby a change in the thickness direction was
measured.
EXAMPLES 1 TO 12
[0144] A polyol, a blowing agent and a foam stabilizer were mixed
in a blend ratio as identified in Table 1 to prepare Premix A. 47.1
g of Premix A was taken into a 300 ml polyethylene cup, and a
catalyst as identified in Table 1 was added in an amount such that
the reactivity as represented by the following gel time would be 90
seconds, whereupon the temperature was adjusted to 10.degree. C. A
polyisocyanate liquid (MR-200) having the temperature adjusted to
10.degree. C. in a separate container, was put into the cup of
Premix A in such an amount that the isocyanate index [isocyanate
groups/OH groups (molar ratio).times.100)] would be 110, and
immediately stirred by a stirrer at 6,500 rpm for 5 seconds. The
mixed and stirred liquid was transferred to a 2 liter polyethylene
cup having the temperature adjusted to 40.degree. C., and the
reactivity during foaming was measured. Then, the starting material
scale was increased, and in the same manner, the mixed liquid was
put into a mold having the temperature adjusted to 40.degree. C.,
whereupon foam molding was carried out. Upon expiration of 10
minutes from the introduction of the mixed liquid, the foam was
removed from the mold. From the molded foam, the flowability, core
density, adhesive strength and dimensional stability of the foam
were evaluated. The results are shown in Table 2. TABLE-US-00001
TABLE 1 Examples 1 2 3 4 5 6 7 8 Blend Premix A Polyol.sup.1) 100
100 100 100 100 100 100 100 (parts by weight) HFC-245fa 30 30 30 30
30 30 30 30 HFC-365mfc Water 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Foam
stabilizer.sup.2) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Amine catalyst
Catalyst A.sup.3) 0.75 0.5 0.7 Catalyst B.sup.4) 0.9 0.6 0.8
Catalyst C.sup.5) 1.0 0.65 Catalyst D.sup.6) Catalyst E.sup.7) 1.5
1.8 2.0 Catalyst F.sup.8) 1.0 1.2 1.3 Catalyst G.sup.9) 1.4 1.6
Isocyanate INDEX.sup.10) 110 110 110 110 110 110 110 110 Examples 9
10 11 12 13 14 15 16 Blend Premix A Polyol.sup.1) 100 100 100 100
100 100 100 100 (parts by weight) HFC-245fa 30 30 30 30 HFC-365mfc
30 30 30 30 Water 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Foam
stabilizer.sup.2) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Amine catalyst
Catalyst A.sup.3) 0.5 0.35 0.45 Catalyst B.sup.4) 0.6 Catalyst
C.sup.5) 0.9 Catalyst D.sup.6) 1.2 0.8 1.1 Catalyst E.sup.7) 2.4
1.0 1.2 Catalyst F.sup.8) 1.6 0.7 Catalyst G.sup.9) 1.8 2.2 0.9
Isocyanate INDEX.sup.10) 110 110 110 110 110 110 110 110 Examples
17 18 19 20 21 22 23 24 Blend Premix A Polyol.sup.1) 100 100 100
100 100 100 100 100 (parts by weight) HFC-245fa HFC-365mfc 30 30 30
30 30 30 30 30 Water 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Foam
stabilizer.sup.2) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Amine catalyst
Catalyst A.sup.3) Catalyst B.sup.4) 0.4 0.5 Catalyst C.sup.5) 0.65
0.4 0.6 Catalyst D.sup.6) 0.8 0.5 0.7 Catalyst E.sup.7) 1.3 1.6
Catalyst F.sup.8) 0.8 0.8 1.0 Catalyst G.sup.9) 1.0 1.2 1.4
Isocyanate INDEX.sup.10) 110 110 110 110 110 110 110 110
.sup.1)Sucrose/aromatic amine type polyether polyol (OH value = 440
mgKOH/g, manufactured by Asahi Glass Company, Limited)
.sup.2)Silicone type surfactant (tradename: SZ-1627), manufactured
by Nippon Unicar Co., Ltd. .sup.3)N,N-dimethylbutylamine
(manufactured by Aldrich Co.) .sup.4)N,N-dimethylhexylamine
(manufactured by Aldrich Co.) .sup.5)N,N-dimethyloctylamine
(manufactured by Tokyo Kasei K.K.) .sup.6)N,N-dimethyldodecylamine
(manufactured by Tokyo Kasei K.K.) .sup.7)Dipropylene glycol
solution containing 33 wt % of triethylenediamine (TEDA-L33,
manufactured by TOSOH CORPORATION)
.sup.8)N,N,N',N'-tetramethyl-1,6-hexanediamine (TOYOCAT-MR,
manufactured by TOSOH CORPORATION)
.sup.9)N,N-dimethylcyclohexylamine (manufactured by Aldrich Co.)
.sup.10)Crude MDI (MR-200), manufactured by Nippon Polyurethane
K.K., INDEX = (mols of NCO groups/mols of OH groups) .times.
100
[0145] TABLE-US-00002 TABLE 2 Examples 1 2 3 4 5 6 7 8 Reactivity
(sec) Cream time 25 20 21 24 20 21 26 20 Gel time 90 91 90 89 90 90
91 90 Tack free time 129 120 125 128 122 126 128 122 Rise time 144
135 140 142 137 141 143 135 Physical properties of foam Flowability
(cm) 81 82 82 79 81 80 79 83 Core density (kg/m.sup.3) 28.3 27.3
27.4 28.3 27.4 27.5 28.1 27.2 Adhesive strength 1.17 1.29 1.20 1.32
1.45 1.34 1.21 1.33 (kgf/cm.sup.2) Dimensional stability (%) -1.0
-1.3 -1.2 -0.7 -1.2 -1.1 -0.8 -1.1 Examples 9 10 11 12 13 14 15 16
Reactivity (sec) Cream time 20 25 21 21 30 24 26 29 Gel time 89 90
90 91 90 90 90 89 Tack free time 125 126 123 125 130 122 124 128
Rise time 139 139 136 138 148 137 143 145 Physical properties of
foam Flowability (cm) 82 79 83 82 78 80 79 78 Core density
(kg/m.sup.3) 27.4 28.4 27.5 27.3 29.5 28.5 28.6 29.5 Adhesive
strength 1.23 1.14 1.28 1.22 1.26 1.48 1.40 1.42 (kgf/cm.sup.2)
Dimensional stability (%) -1.2 -0.9 -1.3 -1.5 -0.9 -1.2 -1.2 -0.7
Examples 17 18 19 20 21 22 23 24 Reactivity (sec) Cream time 25 26
32 24 25 31 26 26 Gel time 91 91 91 89 90 90 90 90 Tack free time
123 127 130 124 126 128 125 128 Rise time 138 141 149 137 140 146
138 143 Physical properties of foam Flowability (cm) 79 79 78 80 79
78 81 80 Core density (kg/m.sup.3) 28.6 28.3 29.3 28.4 28.7 29.6
28.7 28.6 Adhesive strength 1.66 1.57 1.30 1.52 1.44 1.25 1.43 1.34
(kgf/cm.sup.2) Dimensional -1.1 -1.0 -0.7 -1.0 -1.2 -0.8 -1.2 -1.4
stability (%)
COMPARATIVE EXAMPLES 1 TO 7
[0146] A polyol, a blowing agent and a foam stabilizer were mixed
in a blend ratio as identified in Table 3 to prepare Premix A. 47.1
g of Premix A was taken into a 300 ml polyethylene cup, and a
catalyst as identified in Table 3 was added in an amount such that
the reactivity as represented by the following gel time would be 90
seconds, whereupon the temperature was adjusted to 10.degree. C. A
polyisocyanate liquid (MR-200) having the temperature adjusted to
10.degree. C in a separate container, was put into the cup of
Premix A in such an amount that the isocyanate index [isocyanate
groups/OH groups (molar ratio).times.100)] would be 110, and
immediately stirred by a stirrer at 6,500 rpm for 5 seconds. The
mixed and stirred liquid was transferred to a 2 liter polyethylene
cup having the temperature adjusted to 40.degree. C., and the
reactivity during foaming was measured. Then, the starting material
scale was increased, and in the same manner, the mixed liquid was
put into a mold having the temperature adjusted to 40.degree. C.,
whereupon foam molding was carried out. Upon expiration of 10
minutes from the introduction of the mixed liquid, the foam was
removed from the mold. From the molded foam, the flowability, core
density, adhesive strength and dimensional stability of the foam
were evaluated. The results are shown in Table 4. TABLE-US-00003
TABLE 3 Comparative Examples 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Blend
Premix Polyol.sup.1) 100 100 100 100 100 100 100 100 100 100 100
100 100 100 (parts A HFC-245fa 30 30 30 30 30 30 30 by HFC-365mfc
30 30 30 30 30 30 30 weight) Water 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5
2.5 2.5 2.5 2.5 2.5 2.5 Foam stabilizer.sup.2) 2.0 2.0 2.0 2.0 2.0
2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Amine Catalyst A.sup.3) 3.0 2.0
catalyst Catalyst B.sup.4) 3.5 2.3 Catalyst C.sup.5) 4.0 2.6
Catalyst D.sup.6) 4.8 3.1 Catalyst E.sup.7) 2.9 1.9 Catalyst
F.sup.8) 2.1 1.4 Catalyst G.sup.9) 2.8 1.8 Isocyanate INDEX.sup.10)
110 110 110 110 110 110 110 110 110 110 110 110 110 110
.sup.1)Sucrose/aromatic amine type polyether polyol (OH value = 440
mgKOH/g, manufactured by Asahi Glass Company, Limited)
.sup.2)Silicone type surfactant (tradename: SZ-1627), manufactured
by Nippon Unicar Co., Ltd. .sup.3)N,N-dimethylbutylamine
(manufactured by Aldrich Co.) .sup.4)N,N-dimethylhexylamine
(manufactured by Aldrich Co.) .sup.5)N,N-dimethyloctylamine
(manufactured by Tokyo Kasei K.K.) .sup.6)N,N-dimethyldodecylamine
(manufactured by Tokyo Kasei K.K.) .sup.7)Dipropylene glycol
solution containing 33 wt % of triethylenediamine (TEDA-L33,
manufactured by TOSOH CORPORATION)
.sup.8)N,N,N',N'-tetramethyl-1,6-hexanediamine (TOYOCAT-MR,
manufactured by TOSOH CORPORATION)
.sup.9)N,N-dimethylcyclohexylamine (manufactured by Aldrich Co.)
.sup.10)Crude MDI (MR-200), manufactured by Nippon Polyurethane
K.K., INDEX = (mols of NCO groups/mols of OH groups) .times.
100
[0147] TABLE-US-00004 TABLE 4 Comparative Examples 1 2 3 4 5 6 7 8
9 10 11 12 13 14 Reactivity (sec) Cream time 20 20 21 21 25 20 20
24 23 25 26 30 24 25 Gel time 90 90 90 90 90 90 91 90 89 90 90 90
90 91 Tack free time 160 138 143 137 129 130 127 168 145 150 144
136 137 133 Rise time 141 147 154 153 143 142 140 155 154 162 160
150 148 146 Physical properties of foam Flowability 76 77 75 76 72
76 76 75 75 75 76 72 75 76 (cm) Core density 27.5 27.4 27.5 27.3
28.6 27.4 27.5 28.6 28.5 28.4 28.6 29.7 28.5 28.6 (kg/m.sup.3)
Adhesive 1.38 1.56 1.50 1.41 0.45 0.51 0.48 1.62 1.75 1.68 1.55
0.67 0.76 0.72 strength (kgf/cm.sup.2) Dimensional -8.8 -9.2 -8.5
-7.7 -3.5 -5.2 -5.6 -8.2 -7.5 -7.8 -7.2 -2.7 -4.3 -4.4 stability
(%)
EXAMPLES 13 TO 24
[0148] A polyol, a blowing agent and a foam stabilizer were mixed
in a blend ratio as identified in Table 1 to prepare Premix A. 47.1
g of Premix A was taken into a 300 ml polyethylene cup, and a
catalyst as identified in Table 1 was added in an amount such that
the reactivity as represented by the following gel time would be 90
seconds, whereupon the temperature was adjusted to 10.degree. C. A
polyisocyanate liquid (MR-200) having the temperature adjusted to
10.degree. C. in a separate container, was put into the cup of
Premix A in such an amount that the isocyanate index [isocyanate
groups/OH groups (molar ratio).times.100)] would be 110, and
immediately stirred by a stirrer at 6,500 rpm for 5 seconds. The
mixed and stirred liquid was transferred to a 2 liter polyethylene
cup having the temperature adjusted to 40.degree. C., and the
reactivity during foaming was measured. Then, the starting material
scale was increased, and in the same manner, the mixed liquid was
put into a mold having the temperature adjusted to 40.degree. C.,
whereupon foam molding was carried out. Upon expiration of 10
minutes from the introduction of the mixed liquid, the foam was
removed from the mold. From the molded foam, the flowability, core
density, adhesive strength and dimensional stability of the foam
were evaluated. The results are shown in Table 2.
COMPARATIVE EXAMPLES 8 TO 14
[0149] A polyol, a blowing agent and a foam stabilizer were mixed
in a blend ratio as identified in Table 3 to prepare Premix A. 47.1
g of Premix A was taken into a 300 ml polyethylene cup, and a
catalyst as identified in Table 3 was added in an amount such that
the reactivity as represented by the following gel time would be 90
seconds, whereupon the temperature was adjusted to 20.degree. C. A
polyisocyanate liquid (MR-200) having the temperature adjusted to
20.degree. C. in a separate container, was put into the cup of
Premix A in such an amount that the isocyanate index [isocyanate
groups/OH groups (molar ratio).times.100)] would be 110, and
immediately stirred by a stirrer at 6,500 rpm for 5 seconds. The
mixed and stirred liquid was transferred to a 2 liter polyethylene
cup having the temperature adjusted to 40.degree. C., and the
reactivity during foaming was measured. Then, the starting material
scale was increased, and in the same manner, the mixed liquid was
put into a mold having the temperature adjusted to 40.degree. C.,
whereupon foam molding was carried out. Upon expiration of 10
minutes from the introduction of the mixed liquid, the foam was
removed from the mold. From the molded foam, the flowability, core
density, adhesive strength and dimensional stability of the foam
were evaluated. The results are shown in Table 4.
COMPARATIVE EXAMPLES 15 TO 29
[0150] A polyol, a blowing agent and a foam stabilizer were mixed
in a blend ratio as identified in Table 5 to prepare Premix A. 47.1
g of Premix A was taken into a 300 ml polyethylene cup, and a
catalyst as identified in Table 5 was added in an amount such that
the reactivity as represented by the following gel time would be 90
seconds, whereupon the temperature was adjusted to 20.degree. C. A
polyisocyanate liquid (MR-200) having the temperature adjusted to
20.degree. C. in a separate container, was put into the cup of
Premix A in such an amount that the isocyanate index [isocyanate
groups/OH groups (molar ratio).times.100)] would be 110, and
immediately stirred by a stirrer at 6,500 rpm for 5 seconds. The
mixed and stirred liquid was transferred to a 2 liter polyethylene
cup having the temperature adjusted to 40.degree. C., and the
reactivity during foaming was measured. Then, the starting material
scale was increased, and in the same manner, the mixed liquid was
put into a mold having the temperature adjusted to 40.degree. C.,
whereupon foam molding was carried out. Upon expiration of 10
minutes from the introduction of the mixed liquid, the foam was
removed from the mold. From the molded foam, the flowability, core
density, adhesive strength and dimensional stability of the foam
were evaluated. The results are shown in Table 6. TABLE-US-00005
TABLE 5 Comparative Examples 15 16 17 18 19 20 21 22 Blend Premix A
Polyol.sup.1) 100 100 100 100 100 100 100 100 (parts by weight)
HCFC-141b 25 25 25 25 25 25 25 25 Water 2.5 2.5 2.5 2.5 2.5 2.0 2.0
2.0 Foam stabilizer.sup.2) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Amine
catalyst Catalyst A.sup.3) 0.4 0.3 0.4 Catalyst B.sup.4) 0.5 0.35
0.45 Catalyst C.sup.5) 0.55 0.35 Catalyst D.sup.6) Catalyst
E.sup.7) 0.8 1.0 1.1 Catalyst F.sup.8) 0.6 0.7 0.7 Catalyst
G.sup.9) 0.8 0.9 Isocyanate INDEX.sup.10) 110 110 110 110 110 110
110 110 Comparative Examples 23 24 25 26 27 28 29 Blend Premix A
Polyol.sup.1) 100 100 100 100 100 100 100 (parts by weight)
HCFC-141b 25 25 25 25 25 25 25 Water 2.0 2.0 2.0 2.0 2.0 2.0 2.0
Foam stabilizer.sup.2) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Amine catalyst
Catalyst A.sup.3) Catalyst B.sup.4) Catalyst C.sup.5) 0.5 Catalyst
D.sup.6) 0.65 0.45 0.6 Catalyst E.sup.7) 1.3 1.5 Catalyst F.sup.8)
0.9 1.2 Catalyst G.sup.9) 1.0 1.2 1.6 Isocyanate INDEX.sup.10) 110
110 110 110 110 110 110 .sup.1)Sucrose/aromatic amine type
polyether polyol (OH value = 440 mgKOH/g, manufactured by Asahi
Glass Company, Limited) .sup.2)Silicone type surfactant (tradename:
SZ-1627), manufactured by Nippon Unicar Co., Ltd.
.sup.3)N,N-dimethylbutylamine (manufactured by Aldrich Co.)
.sup.4)N,N-dimethylhexylamine (manufactured by Aldrich Co.)
.sup.5)N,N-dimethyloctylamine (manufactured by Tokyo Kasei K.K.)
.sup.6)N,N-dimethyldodecylamine (manufactured by Tokyo Kasei K.K.)
.sup.7)Dipropylene glycol solution containing 33 wt % of
triethylenediamine (TEDA-L33, manufactured by TOSOH CORPORATION)
.sup.8)N,N,N',N'-tetramethyl-1,6-hexanediamine (TOYOCAT-MR,
manufactured by TOSOH CORPORATION)
.sup.9)N,N-dimethylcyclohexylamine (manufactured by Aldrich Co.)
.sup.10)Crude MDI (MR-200), manufactured by Nippon Polyurethane
K.K., INDEX = (mols of NCO groups/mols of OH groups) .times.
100
[0151] TABLE-US-00006 TABLE 6 Comparative Examples 15 16 17 18 19
20 21 22 Reactivity (sec) Cream time 31 25 27 29 24 25 31 25 Gel
time 90 89 90 90 91 90 90 90 Tack free time 131 123 125 129 122 126
130 124 Rise time 146 139 142 143 137 140 145 138 Physical
properties of foam Flowability (cm) 81 84 83 80 83 82 81 83 Core
density (kg/m.sup.3) 29.2 28.2 28.4 29.3 28.3 28.0 29.0 28.2
Adhesive strength (kgf/cm.sup.2) 1.62 1.76 1.71 1.70 1.86 1.79 1.67
1.82 Dimensional stability (%) -1.0 -1.2 -1.3 -0.8 -1.2 -1.1 -0.8
-1.0 Comparative Examples 23 24 25 26 27 28 29 Reactivity (sec)
Cream time 25 30 25 26 31 25 26 Gel time 90 91 90 90 90 90 90 Tack
free time 125 128 126 125 129 125 126 Rise time 139 143 136 139 143
139 140 Physical properties of foam Flowability (cm) 83 80 84 83 81
84 84 Core density (kg/m.sup.3) 28.4 29.3 28.4 28.3 29.3 28.0 28.1
Adhesive strength (kgf/cm.sup.2) 1.75 1.65 1.83 1.72 1.62 1.78 1.70
Dimensional stability (%) -1.2 -0.9 -1.3 -1.5 -0.9 -1.3 -1.2
[0152] As is evident from Tables 2, 4 and 6, it is possible to
produce foams excellent in flowability, adhesive strength and
dimensional stability by using amine compounds of the present
invention as catalysts.
[0153] Namely, Examples 1 to 12 are examples wherein rigid
polyurethane foams were produced by using catalysts of the present
invention and 1,1,1,3,3-pentafluoropropane (HFC-245fa) as a blowing
agent. In each Example, a rigid urethane foam excellent in
flowability, adhesive strength and dimensional stability, was
obtained. Further, Examples 13 to 24 are Examples wherein rigid
polyurethane foams were produced by using the catalysts of the
present invention and 1,1,1,3,3-pentafluorobutane (HFC-365mfc) as a
blowing agent. In each Example, a rigid urethane foam excellent in
flowability, adhesive strength and dimensional stability, was
obtained.
[0154] Whereas, Comparative Examples 1 to 4 and Comparative
Examples 8 to 11 are examples wherein rigid polyurethane foams were
produced by using only the aliphatic amine compounds of the above
formula (1) as catalysts, whereby large amounts of the catalysts
were required, and the foams were inferior in flowability and
dimensional stability.
[0155] Further, Comparative Examples 5 to 7 and Comparative
Examples 12 to 14 are examples wherein rigid polyurethane foams
were produced by using triethylenediamine,
N,N,N',N'-tetramethyl-1,6-hexanediamine or
N,N-dimethylcyclohexylamine solely as the catalyst without using
the aliphatic amine compound of the above formula (1), whereby the
obtained foams were inferior in flowability, adhesive strength and
dimensional stability.
[0156] Further, Comparative Examples 15 to 21 are examples in which
1,1-dichloro-1-fluoroethane (HCFC-141b) was used as a blowing
agent, whereby even if the catalyst of the present invention was
used, no remarkable effect was observed in the flowability,
adhesive strength and dimensional stability of the foams.
EXAMPLES 25 TO 48
[0157] A polyol, a blowing agent and a foam stabilizer were mixed
in a blend ratio as identified in Table 7 to prepare Premix A. 47.1
g of Premix A was taken into a 300 ml polyethylene cup, and a
catalyst as identified in Table 7 was added in an amount such that
the reactivity as represented by the following gel time would be 90
seconds, whereupon the temperature was adjusted to 20.degree. C. A
polyisocyanate liquid (MR-200) having the temperature adjusted to
10.degree. C. in a separate container, was put into the cup of
Premix A in such an amount that the isocyanate index [isocyanate
groups/OH groups (molar ratio).times.100)] would be 110, and
immediately stirred by a stirrer at 6,500 rpm for 5 seconds. The
mixed and stirred liquid was transferred to a 2 liter polyethylene
cup having the temperature adjusted to 40.degree. C., and the
reactivity during foaming was measured. Then, the starting material
scale was increased, and in the same manner, the mixed liquid was
put into a mold having the temperature adjusted to 40.degree. C.,
whereupon foam molding was carried out. Upon expiration of 10
minutes from the introduction of the mixed liquid, the foam was
removed from the mold. From the molded foam, the flowability, core
density, adhesive strength and dimensional stability of the foam
were evaluated. The results are shown in Table 8. TABLE-US-00007
TABLE 7 Examples 25 26 27 28 29 30 31 32 Blend Premix A Polyol
A.sup.1) 80 80 80 80 80 80 80 80 (parts by weight) Polyol B.sup.2)
20 20 20 20 20 20 20 20 Cyclopentane 16 16 16 16 16 16 16 16
Isopentane Water 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Foam
stabilizer.sup.3) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Amine catalyst
Catalyst A.sup.4) 0.38 0.25 0.35 Catalyst B.sup.5) 0.45 0.30 0.80
Catalyst C.sup.6) 0.50 0.33 Catalyst D.sup.7) Catalyst E.sup.8)
0.75 0.90 1.00 Catalyst F.sup.9) 0.50 0.60 0.65 Catalyst G.sup.10)
0.70 1.60 Isocyanate INDEX.sup.11) 110 110 110 110 110 110 110 110
Examples 33 34 35 36 37 38 39 40 Blend Premix A Polyol A.sup.1) 80
80 80 80 80 80 80 80 (parts by weight) Polyol B.sup.2) 20 20 20 20
20 20 20 20 Cyclopentane 16 16 16 16 10 10 10 10 Isopentane 4 4 4 4
Water 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Foam stabilizer.sup.3) 1.5
1.5 1.5 1.5 1.5 1.5 1.5 1.5 Amine catalyst Catalyst A.sup.4) 0.35
0.23 0.33 Catalyst B.sup.5) 0.40 Catalyst C.sup.6) 0.45 Catalyst
D.sup.7) 0.60 0.40 0.55 Catalyst E.sup.8) 1.20 0.70 0.80 Catalyst
F.sup.9) 0.80 0.45 Catalyst G.sup.10) 0.90 1.10 0.65 Isocyanate
INDEX.sup.11) 110 110 110 110 110 110 110 110 Examples 41 42 43 44
45 46 47 48 Blend Premix A Polyol A.sup.1) 80 80 80 80 80 80 80 80
(parts by weight) Polyol B.sup.2) 20 20 20 20 20 20 20 20
Cyclopentane 10 10 10 10 10 10 10 10 Isopentane 4 4 4 4 4 4 4 4
Water 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Foam stabilizer.sup.3) 1.5
1.5 1.5 1.5 1.5 1.5 1.5 1.5 Amine catalyst Catalyst A.sup.4)
Catalyst B.sup.5) 0.28 0.70 Catalyst C.sup.6) 0.45 0.30 0.40
Catalyst D.sup.7) 0.55 0.35 0.50 Catalyst E.sup.8) 0.90 1.10
Catalyst F.sup.9) 0.55 0.60 0.70 Catalyst G.sup.10) 1.40 0.80 1.00
Isocyanate INDEX.sup.11) 110 110 110 110 110 110 110 110
.sup.1)Waste PET type polyester polyol (OH value = 241 mgKOH/g)
manufactured by Oxid Co. .sup.2)Mannich type polyether polyol (OH
value = 469 mgKOH/g) manufactured by Daiichi Kogyo Seiyaku Co.,
Ltd. .sup.3)Silicone type surfactant (tradename: L-5420),
manufactured by Nippon Unicar Co., Ltd.
.sup.4)N,N-dimethylbutylamine (manufactured by Aldrich Co.)
.sup.5)N,N-dimethylhexylamine (manufactured by Aldrich Co.)
.sup.6)N,N-dimethyloctylamine (manufactured by Tokyo Kasei K.K.)
.sup.7)N,N-dimethyldodecylamine (manufactured by Tokyo Kasei K.K.)
.sup.8)Dipropylene glycol solution containing 33 wt % of
triethylenediamine (TEDA-L33, manufactured by TOSOH CORPORATION)
.sup.9)N,N,N',N'-tetramethyl-1,6-hexanediamine (TOYOCAT-MR,
manufactured by TOSOH CORPORATION)
.sup.10)N,N-dimethylcyclohexylamine (manufactured by Aldrich Co.)
.sup.11)Crude MDI (MR-200), manufactured by Nippon Polyurethane
K.K., INDEX = (mols of NCO groups/mols of OH groups) .times.
100
[0158] TABLE-US-00008 TABLE 8 Examples 25 26 27 28 29 30 31 32 33
34 35 36 Reactivity (sec) Cream time 30 25 26 29 25 26 31 25 25 30
26 26 Gel time 90 90 91 90 89 90 91 90 90 91 90 90 Tack free time
150 143 143 148 143 143 150 143 144 148 145 144 Rise time 161 147
153 155 148 151 158 148 150 157 148 153 Physical properties of foam
Flowability (cm) 78 79 80 76 78 78 76 80 79 76 80 79 Core density
(kg/m.sup.3) 31.6 30.4 30.6 31.6 30.6 30.7 31.3 30.3 30.6 31.7 30.7
30.4 Adhesive strength 1.64 1.81 1.68 1.85 2.03 1.88 1.69 1.86 1.72
1.6 1.79 1.71 (kgf/cm.sup.2) Dimensional -0.9 -1.2 -1.1 -0.6 -1.1
-1.0 -0.7 -1.0 -1.1 -0.8 -1.2 -1.4 stability (%) Examples 37 38 39
40 41 42 43 44 45 46 47 48 Reactivity (sec) Cream time 29 24 25 28
24 25 30 24 24 29 25 25 Gel time 89 90 90 91 90 90 90 90 89 91 90
90 Tack free time 151 140 145 148 142 143 149 143 143 149 143 144
Rise time 162 145 150 159 148 151 155 145 150 158 146 148 Physical
properties of foam Flowability (cm) 79 80 81 77 79 79 77 81 80 77
81 80 Core density (kg/m.sup.3) 30.7 29.5 29.7 30.7 29.7 29.8 30.4
29.4 29.7 30.8 29.8 29.5 Adhesive strength 1.59 1.76 1.63 1.80 1.97
1.82 1.64 1.80 1.67 1.55 1.74 1.66 (kgf/cm.sup.2) Dimensional -0.8
-1.1 -1.0 -0.5 -1.0 -0.9 -0.6 -0.9 -1.0 -0.7 -1.1 -1.3 stability
(%)
COMPARATIVE EXAMPLES 30 TO 43
[0159] A polyol, a blowing agent and a foam stabilizer were mixed
in a blend ratio as identified in Table 9 to prepare Premix A. 47.1
g of Premix A was taken into a 300 ml polyethylene cup, and a
catalyst as identified in Table 9 was added in an amount such that
the reactivity as represented by the following gel time would be 90
seconds, whereupon the temperature was adjusted to 20.degree. C. A
polyisocyanate liquid (MR-200) having the temperature adjusted to
20.degree. C. in a separate container, was put into the cup of
Premix A in such an amount that the isocyanate index [isocyanate
groups/OH groups (molar ratio) x 100)] would be 110, and
immediately stirred by a stirrer at 6,500 rpm for 5 seconds. The
mixed and stirred liquid was transferred to a 2 liter polyethylene
cup having the temperature adjusted to 40.degree. C., and the
reactivity during foaming was measured. Then, the starting material
scale was increased, and in the same manner, the mixed liquid was
put into a mold having the temperature adjusted to 40.degree. C.,
whereupon foam molding was carried out. Upon expiration of 10
minutes from the introduction of the mixed liquid, the foam was
removed from the mold. From the molded foam, the flowability, core
density, adhesive strength and dimensional stability of the foam
were evaluated. The results are shown in Table 10. TABLE-US-00009
TABLE 9 Comparative Examples 30 31 32 33 34 35 36 Blend Premix A
Polyol A.sup.1) 80 80 80 80 80 80 80 (parts by weight) Polyol
B.sup.2) 20 20 20 20 20 20 20 Cyclopentane 16 16 16 16 16 16 16
Isopentane Water 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Foam stabilizer.sup.3)
1.5 1.5 1.5 1.5 1.5 1.5 1.5 Amine catalyst Catalyst A.sup.4) 1.60
Catalyst B.sup.5) 1.85 Catalyst C.sup.6) 2.10 Catalyst D.sup.7)
2.55 Catalyst E.sup.8) 1.55 Catalyst F.sup.9) 1.10 Catalyst
G.sup.10) 1.45 Isocyanate INDEX.sup.11) 110 110 110 110 110 110 110
Comparative Examples 37 38 39 40 41 42 43 Blend Premix A Polyol
A.sup.1) 80 80 80 80 80 80 80 (parts by weight) Polyol B.sup.2) 20
20 20 20 20 20 20 Cyclopentane 10 10 10 10 10 10 10 Isopentane 4 4
4 4 4 4 4 Water 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Foam stabilizer.sup.3)
1.5 1.5 1.5 1.5 1.5 1.5 1.5 Amine catalyst Catalyst A.sup.4) 1.45
Catalyst B.sup.5) 1.65 Catalyst C.sup.6) 1.90 Catalyst D.sup.7)
2.30 Catalyst E.sup.8) 1.40 Catalyst F.sup.9) 1.05 Catalyst
G.sup.10) 1.30 Isocyanate INDEX.sup.11) 110 110 110 110 110 110 110
.sup.1)Waste PET type polyester polyol (OH value = 241 mgKOH/g)
manufactured by Oxid Co. .sup.2)Mannich type polyether polyol (OH
value = 469 mgKOH/g) manufactured by Daiichi Kogyo Seiyaku Co.,
Ltd. .sup.3)Silicone type surfactant (tradename: L-5420),
manufactured by Nippon Unicar Co., Ltd.
.sup.4)N,N-dimethylbutylamine (manufactured by Aldrich Co.)
.sup.5)N,N-dimethylhexylamine (manufactured by Aldrich Co.)
.sup.6)N,N-dimethyloctylamine (manufactured by Tokyo Kasei K.K.)
.sup.7)N,N-dimethyldodecylamine (manufactured by Tokyo Kasei K.K.)
.sup.8)Dipropylene glycol solution containing 33 wt % of
triethylenediamine (TEDA-L33, manufactured by TOSOH CORPORATION)
.sup.9)N,N,N',N'-tetramethyl-1,6-hexanediamine (TOYOCAT-MR,
manufactured by TOSOH CORPORATION)
.sup.10)N,N-dimethylcyclohexylamine (manufactured by Aldrich Co.)
.sup.11)Crude MDI (MR-200), manufactured by Nippon Polyurethane
K.K., INDEX = (mols of NCO groups/mols of OH groups) .times.
100
[0160] TABLE-US-00010 TABLE 10 Comparative Examples 30 31 32 33 34
35 36 37 38 39 40 41 42 43 Reactivity (sec) Cream time 25 24 26 25
30 25 26 24 24 25 24 29 24 25 Gel time 90 91 90 90 89 90 90 90 90
90 91 89 90 90 Tack free time 145 143 148 142 150 140 143 143 143
146 140 151 143 141 Rise time 156 157 159 153 162 155 160 155 156
157 155 160 158 156 Physical properties of foam Flowability 73 74
72 73 70 73 73 74 75 73 74 70 74 74 (cm) Core 32.2 32.1 32.2 32.0
33.5 32.1 32.2 31.9 31.8 31.9 31.6 33.2 31.8 31.9 density
(kg/m.sup.3) Adhesive 1.79 2.03 1.95 1.83 0.90 1.02 0.96 1.74 1.95
1.88 1.78 0.88 1.00 0.95 strength (kgf/cm.sup.2) Dimensional -7.7
-8.1 -7.5 -6.8 -3.1 -4.6 -5.0 -6.8 -7.2 -6.8 -6.0 -2.8 -4.3 -4.3
stability (%)
COMPARATIVE EXAMPLES 44 TO 58
[0161] A polyol, a blowing agent and a foam stabilizer were mixed
in a blend ratio as identified in Table 11 to prepare Premix A.
47.1 g of Premix A was taken into a 300 ml polyethylene cup, and a
catalyst as identified in Table 11 was added in an amount such that
the reactivity as represented by the following gel time would be 90
seconds, whereupon the temperature was adjusted to 20.degree. C. A
polyisocyanate liquid (MR-200) having the temperature adjusted to
20.degree. C. in a separate container, was put into the cup of
Premix A in such an amount that the isocyanate index [isocyanate
groups/OH groups (molar ratio).times.100)] would be 110, and
immediately stirred by a stirrer at 6,500 rpm for 5 seconds. The
mixed and stirred liquid was transferred to a 2 liter polyethylene
cup having the temperature adjusted to 40.degree. C., and the
reactivity during foaming was measured. Then, the starting material
scale was increased, and in the same manner, the mixed liquid was
put into a mold having the temperature adjusted to 40.degree. C.,
whereupon foam molding was carried out. Upon expiration of 10
minutes from the introduction of the mixed liquid, the foam was
removed from the mold. From the molded foam, the flowability, core
density, adhesive strength and dimensional stability of the foam
were evaluated. The results are shown in Table 12. TABLE-US-00011
TABLE 11 Comparative Example 44 45 46 47 48 49 50 51 Blend Premix A
Polyol A.sup.1) 80 80 80 80 80 80 80 80 (parts by Polyol B.sup.2)
20 20 20 20 20 20 20 20 weight) HCFC-141b 25 25 25 25 25 25 25 25
Water 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Foam stabilizer.sup.3) 1.5
1.5 1.5 1.5 1.5 1.5 1.5 1.5 Amine Catalyst A.sup.4) 0.35 0.25 0.35
catalyst Catalyst B.sup.5) 0.45 0.33 0.40 Catalyst C.sup.6) 0.50
0.30 Catalyst D.sup.7) Catalyst E.sup.8) 0.70 0.90 1.0 Catalyst
F.sup.9) 0.50 0.65 0.60 Catalyst G.sup.10) 0.70 0.80 Isocyanate
INDEX.sup.11) 110 110 110 110 110 110 110 110 Comparative Example
52 53 54 55 56 57 58 Blend Premix A Polyol A.sup.1) 80 80 80 80 80
80 80 (parts by Polyol B.sup.2) 20 20 20 20 20 20 20 weight)
HCFC-141b 25 25 25 25 25 25 25 Water 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Foam stabilizer.sup.3) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Amine Catalyst
A.sup.4) catalyst Catalyst B.sup.5) Catalyst C.sup.6) 0.45 Catalyst
D.sup.7) 0.60 0.40 0.55 Catalyst E.sup.8) 1.20 1.35 Catalyst
F.sup.9) 0.80 1.10 Catalyst G.sup.10) 0.90 1.10 1.45 Isocyanate
INDEX.sup.11) 110 110 110 110 110 110 110 .sup.1)Waste PET type
polyester polyol (OH value = 241 mgKOH/g) manufactured by Oxide Co.
.sup.2)Mannich type polyether polyol (OH value = 469 mgKOH/g)
manufactured by Daiichi Kogyo Seiyaku Co., Ltd. .sup.3)Silicone
type surfactant (tradename: L-5420), manufactured by Nippon Unicar
Co., Ltd. .sup.4)N,N-dimethylbutylamine (manufactured by Aldrich
Co.) .sup.5)N,N-dimethylhexylamine (manufactured by Aldrich Co.)
.sup.6)N,N-dimethyloctylamine (manufactured by Tokyo Kasei K.K.)
.sup.7)N,N-dimethyldodecylamine (manufactured by Tokyo Kasei K.K.)
.sup.8)Dipropylene glycol solution containing 33 wt % of
triethylenediamine (TEDA-L33, manufactured by TOSOH CORPORATION)
.sup.9)N,N,N',N'-tetramethyl-1,6-hexanediamine (TOYOCAT-MR,
manufactured by TOSOH CORPORATION)
.sup.10)N,N-dimethylcyclohexylamine (manufactured by Aldrich Co.)
.sup.11)Crude MDI (MR-200), manufactured by Nippon Polyurethane
K.K., INDEX = (mols of NCO groups/mols of OH groups) .times.
100
[0162] TABLE-US-00012 TABLE 12 Comparative Examples 44 45 46 47 48
49 50 51 Reactivity (sec) Cream time 30 24 25 28 24 24 30 24 Gel
time 90 90 91 90 90 89 90 91 Tack free time 152 143 145 150 143 144
150 144 Rise time 166 139 142 143 137 140 145 138 Physical
properties of foam Flowability (cm) 78 81 80 77 80 79 78 80 Core
density (kg/m.sup.3) 30.4 29.4 29.6 30.5 29.5 29.2 30.2 29.4
Adhesive strength 1.64 1.78 1.73 1.72 1.88 1.81 1.69 1.84
(kgf/cm.sup.2) Dimensional stability (%) -1.1 -1.4 -1.5 -0.9 -1.3
-0.1 -0.9 -1.1 Comparative Examples 52 53 54 55 56 57 58 Reactivity
(sec) Cream time 25 29 24 25 30 24 25 Gel time 90 90 89 90 90 91 90
Tack free time 145 148 143 145 150 145 146 Rise time 139 143 136
139 143 139 140 Physical properties of foam Flowability (cm) 80 77
81 80 78 81 81 Core density (kg/m.sup.3) 29.6 30.5 29.6 29.5 30.5
29.2 29.3 Adhesive strength 1.77 1.67 1.85 1.74 1.64 1.80 1.72
(kgf/cm.sup.2) Dimensional stability (%) -1.3 -0.9 -1.4 -1.5 -1.0
-1.4 -1.3
[0163] As is evident from Tables 8, 10 and 12, it is possible to
produce foams excellent in flowability, adhesive strength and
dimensional stability by using amine compounds of the present
invention as catalysts.
[0164] Namely, Examples 25 to 48 are examples wherein rigid
polyurethane foams were produced by using low boiling point
hydrocarbons having boiling points of from -30 to 90.degree. C. as
blowing agents. In each Example, a rigid urethane foam excellent in
flowability, adhesive strength and dimensional stability, was
obtained.
[0165] Whereas, Comparative Examples 30 to 33 and Comparative
Examples 37 to 40 are examples wherein rigid polyurethane foams
were produced by using only the aliphatic amine compounds of the
above formula (1) as catalysts, whereby large amounts of the
catalysts were required, and the foams were inferior in flowability
and dimensional stability.
[0166] Further, Comparative Examples 34 to 36 and Comparative
Examples 41 to 43 are examples wherein rigid polyurethane foams
were produced by using triethylenediamine,
N,N,N',N'-tetramethyl-1,6-hexanediamine or
N,N-dimethylcyclohexylamine solely as the catalyst without using
the aliphatic amine compound of the above formula (1), whereby the
foams were inferior in flowability, adhesive strength and
dimensional stability.
[0167] Further, Comparative Examples 44 to 58 are examples in which
1,1-dichloro-1-fluoroethane (HCFC-141b) was used as a blowing
agent, whereby even if the catalyst of the present invention was
used, no distinct effect to the flowability, adhesive strength and
dimensional stability, was observed.
EXAMPLES 49 TO 52 AND COMPARATIVE EXAMPLES 59 TO 61
[0168] A polyol, a blowing agent and a foam stabilizer were mixed
in a blend ratio as identified in Table 13 to prepare Premix A.
47.1 g of Premix A was taken into a 300 ml polyethylene cup, and a
catalyst as identified in Table 13 was added in an amount such that
the reactivity as represented by the following gel time would be 90
seconds, whereupon the temperature was adjusted to 10.degree. C. A
polyisocyanate liquid (MR-200) having the temperature adjusted to
10.degree. C. in a separate container, was put into the cup of
Premix A in such an amount that the isocyanate index [isocyanate
groups/OH groups (molar ratio).times.100)] would be 110, and
immediately stirred by a stirrer at 6,500 rpm for 5 seconds. The
mixed and stirred liquid was transferred to a 2 liter polyethylene
cup having the temperature adjusted to 40.degree. C., and the
reactivity during foaming was measured. Then, the starting material
scale was increased, and in the same manner, the mixed liquid was
put into a mold having the temperature adjusted to 40.degree. C.,
whereupon foam molding was carried out. Upon expiration of 10
minutes from the introduction of the mixed liquid, the foam was
removed from the mold. From the molded foam, the flowability, core
density, adhesive strength and dimensional stability of the foam
were evaluated. The results are shown in Table 14. TABLE-US-00013
TABLE 13 Comparative Examples Examples 49 50 51 52 59 60 61 Blend
Premix A Polyol.sup.1) 100 100 100 100 100 100 100 (parts by
HFC-245fa 30 30 30 30 30 30 30 weight) Water 2.5 2.5 2.5 2.5 2.5
2.5 2.5 Foam stabilizer.sup.2) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Amine
catalyst Catalyst A.sup.3) 6.0 Catalyst B.sup.4) 6.8 Catalyst
C.sup.5) 3.4 Catalyst D.sup.6) 8.5 Catalyst E.sup.7) 2.9 Catalyst
F.sup.8) 2.1 Catalyst G.sup.9) 2.8 Isocyanate INDEX.sup.10) 110 110
110 110 110 110 110 .sup.1)Sucrose/aromatic amine type polyether
polyol (OH value = 440 mgKOH/g, manufactured by Asahi Glass
Company, Limited) .sup.2)Silicone type surfactant (tradename:
SZ-1627), manufactured by Nippon Unicar Co., Ltd.
.sup.3)N,N-dimethylaminoethyl methyl ether (Product obtained by
reacting N,N-dimethylaminoethanol with methyl iodide)
.sup.4)N,N-dimethylaminoethyl ethyl ether (Product obtained by
reacting N,N-dimethylaminoethanol with ethyl bromide)
.sup.5)N,N-dimethylaminohexyl methyl ether (Product obtained by
reacting N,N-dimethylaminohexanol with methyl iodide)
.sup.6)N-(2-methoxyethyl)-N'-methylpiperazine (Product obtained by
reacting N-(2-hydroxyethyl)-N'-methylpiperazine with methyl iodide)
.sup.7)Dipropylene glycol solution containing 33 wt % of
triethylenediamine (TEDA-L33, manufactured by TOSOH CORPORATION)
.sup.8)N,N,N',N'-tetramethylhexamethylenediamine (TOYOCAT-MR,
manufactured by TOSOH CORPORATION)
.sup.9)N,N-dimethylcyclohexylamine (manufactured by Aldrich Co.)
.sup.10)Crude MDI (MR-200), manufactured by Nippon Polyurethane
K.K., INDEX = (mols of NCO groups/mols of OH groups) .times.
100
[0169] TABLE-US-00014 TABLE 14 Comparative Examples Examples 49 50
51 52 59 60 61 Reactivity (sec) Cream time 23 22 20 21 25 20 20 Gel
time 91 90 90 91 90 90 91 Tack free time 151 146 135 148 129 130
127 Rise time 158 155 148 155 143 142 140 Physical properties of
foam Flowability (cm) 83 82 80 81 72 76 76 Core density
(kg/m.sup.3) 27.3 27.3 27.4 27.6 28.6 27.4 27.5 Adhesive strength
1.14 1.18 1.25 0.96 0.45 0.51 0.48 (kgf/cm.sup.2) Dimensional
stability -1.2 -1.1 -1.0 -1.5 -3.5 -5.2 -5.6 (%)
[0170] As is evident from Table 14, it is possible to produce foams
excellent in flowability, adhesive strength and dimensional
stability by using amine compounds of the present invention-as
catalysts.
[0171] Namely, Examples 49 to 52 are examples wherein rigid
polyurethane foams were produced by using the catalysts of the
present invention. In each Example, a rigid urethane foam excellent
in flowability, adhesive strength and dimensional stability, was
obtained.
[0172] Whereas, Comparative Examples 59 to 61 are examples wherein
tertiary amine catalysts having no alkyl ether group or no aryl
ether group in their molecules, were used, whereby the foams were
inferior in flowability, adhesive strength and dimensional
stability.
EXAMPLES 53 TO 56 AND COMPARATIVE EXAMPLES 62 TO 64
[0173] A polyol, a blowing agent and a foam stabilizer were mixed
in a blend ratio as identified in Table 15 to prepare Premix A.
47.1 g of Premix A was taken into a 300 ml polyethylene cup, and a
catalyst as identified in Table 15 was added in an amount such that
the reactivity as represented by the following gel time would be 90
seconds, whereupon the temperature was adjusted to 20.degree. C. A
polyisocyanate liquid (MR-200) having the temperature adjusted to
20.degree. C. in a separate container, was put into the cup of
Premix A in such an amount that the isocyanate index [isocyanate
groups/OH groups (molar ratio).times.100)] would be 110, and
immediately stirred by a stirrer at 6,500 rpm for 5 seconds. The
mixed and stirred liquid was transferred to a 2 liter polyethylene
cup having the temperature adjusted to 40.degree. C., and the
reactivity during foaming was measured. Then, the starting material
scale was increased, and in the same manner, the mixed liquid was
put into a mold having the temperature adjusted to 40.degree. C.,
whereupon foam molding was carried out. Upon expiration of 10
minutes from the introduction of the mixed liquid, the foam was
removed from the mold. From the molded foam, the flowability, core
density, adhesive strength and dimensional stability of the foam
were evaluated. The results are shown in Table 16. TABLE-US-00015
TABLE 15 Comparative Examples Examples 53 54 55 56 62 63 64 Blend
Premix A Polyol.sup.1) 100 100 100 100 100 100 100 (parts by
weight) HFC-365mfc 30 30 30 30 30 30 30 Water 2.5 2.5 2.5 2.5 2.5
2.5 2.5 Foam stabilizer.sup.2) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Amine
catalyst Catalyst A.sup.3) 3.9 Catalyst B.sup.4) 4.3 Catalyst
C.sup.5) 2.2 Catalyst D.sup.6) 5.4 Catalyst E.sup.7) 1.9 Catalyst
F.sup.8) 1.4 Catalyst G.sup.9) 1.8 Isocyanate INDEX.sup.10) 110 110
110 110 110 110 110 .sup.1)Sucrose/aromatic amine type polyether
polyol (OH value = 440 mgKOH/g, manufactured by Asahi Glass
Company, Limited) .sup.2)Silicone type surfactant (tradename:
SZ-1627), manufactured by Nippon Unicar Co., Ltd.
.sup.3)N,N-dimethylaminoethyl methyl ether (Product obtained by
reacting N,N-dimethylaminoethanol with methyl iodide)
.sup.4)N,N-dimethylaminoethyl ethyl ether (Product obtained by
reacting N,N-dimethylaminoethanol with ethyl bromide)
.sup.5)N,N-dimethylaminohexyl methyl ether (Product obtained by
reacting N,N-dimethylaminohexanol with methyl iodide)
.sup.6)N-(2-methoxyethyl)-N'-methylpiperazine (Product obtained by
reacting N-(2-hydroxyethyl)-N'-methylpiperazine with methyl iodide)
.sup.7)Dipropylene glycol solution containing 33 wt % of
triethylenediamine (TEDA-L33, manufactured by TOSOH CORPORATION)
.sup.8)N,N,N',N'-tetramethylhexamethylenediamine (TOYOCAT-MR,
manufactured by TOSOH CORPORATION)
.sup.9)N,N-dimethylcyclohexylamine (manufactured by Aldrich Co.)
.sup.10)Crude MDI (MR-200), manufactured by Nippon Polyurethane
K.K., INDEX = (mols of NCO groups/mols of OH groups) .times.
100
[0174] TABLE-US-00016 TABLE 16 Comparative Examples Examples 53 54
55 56 62 63 64 Reactivity (sec) Cream time 25 24 21 23 30 24 25 Gel
time 90 90 89 90 90 90 91 Tack free time 155 150 141 153 136 137
133 Rise time 162 159 152 164 150 148 146 Physical properties of
foam Flowability (cm) 81 81 80 80 72 75 76 Core density
(kg/m.sup.3) 28.3 28.4 28.5 28.7 29.7 28.5 28.6 Adhesive strength
1.38 1.43 1.50 1.18 0.67 0.76 0.72 (kgf/cm.sup.2) Dimensional
stability -1.1 -1.1 -0.8 -1.4 -2.7 -4.3 -4.4 (%)
[0175] As is evident from Table 16, it is possible to produce foams
excellent in flowability, adhesive strength and dimensional
stability by using amine compounds of the present invention as
catalysts.
[0176] Namely, Examples 53 to 56 are examples wherein rigid
polyurethane foams were produced by using the catalysts of the
present invention. In each Example, a rigid urethane foam excellent
in flowability, adhesive strength and dimensional stability, was
obtained.
[0177] Whereas, Comparative Examples 62 to 64 are examples wherein
tertiary amine catalysts having no alkyl ether group or no aryl
ether group in their molecules, were used, whereby the foams were
inferior in flowability, adhesive strength and dimensional
stability.
EXAMPLES 57 TO 60 AND COMPARATIVE EXAMPLES 65 TO 67
[0178] A polyol, a blowing agent and a foam stabilizer were mixed
in a blend ratio as identified in Table 17 to prepare Premix A.
47.1 g of Premix A was taken into a 300 ml polyethylene cup, and a
catalyst as identified in Table 17 was added in an amount such that
the reactivity as represented by the following gel time would be 90
seconds, whereupon the temperature was adjusted to 20.degree. C. A
polyisocyanate liquid (MR-200) having the temperature adjusted to
20.degree. C. in a separate container, was put into the cup of
Premix A in such an amount that the isocyanate index [isocyanate
groups/OH groups (molar ratio).times.100)] would be 110, and
immediately stirred by a stirrer at 6,500 rpm for 5 seconds. The
mixed and stirred liquid was transferred to a 2 liter polyethylene
cup having the temperature adjusted to 40.degree. C., and the
reactivity during foaming was measured. Then, the starting material
scale was increased, and in the same manner, the mixed liquid was
put into a mold having the temperature adjusted to 40.degree. C.,
whereupon foam molding was carried out. Upon expiration of 10
minutes from the introduction of the mixed liquid, the foam was
removed from the mold. From the molded foam, the flowability, core
density, adhesive strength and dimensional stability of the foam
were evaluated. The results are shown in Table 18. TABLE-US-00017
TABLE 17 Comparative Examples Examples 57 58 59 60 65 66 67 Blend
Premix A Polyol.sup.1) 100 100 100 100 100 100 100 (parts by
weight) Cyclopentane 15 15 15 15 15 15 15 Water 2.0 2.0 2.0 2.0 2.0
2.0 2.0 Foam stabilizer.sup.2) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Amine
catalyst Catalyst A.sup.3) 3.1 Catalyst B.sup.4) 3.6 Catalyst
C.sup.5) 2.0 Catalyst D.sup.6) 4.3 Catalyst E.sup.7) 1.5 Catalyst
F.sup.8) 1.1 Catalyst G.sup.9) 1.5 Isocyanate INDEX.sup.10) 110 110
110 110 110 110 110 .sup.1)Sucrose/aromatic amine type polyether
polyol (OH value = 440 mgKOH/g, manufactured by Asahi Glass
Company, Limited) .sup.2)Silicone type surfactant (tradename:
SZ-1627), manufactured by Nippon Unicar Co., Ltd.
.sup.3)N,N-dimethylaminoethyl methyl ether (Product obtained by
reacting N,N-dimethylaminoethanol with methyl iodide)
.sup.4)N,N-dimethylaminoethyl ethyl ether (Product obtained by
reacting N,N-dimethylaminoethanol with ethyl bromide)
.sup.5)N,N-dimethylaminohexyl methyl ether (Product obtained by
reacting N,N-dimethylaminohexanol with methyl iodide)
.sup.6)N-(2-methoxyethyl)-N'-methylpiperazine (Product obtained by
reacting N-(2-hydroxyethyl)-N'-methylpiperazine with methyl iodide)
.sup.7)Dipropylene glycol solution containing 33 wt % of
triethylenediamine (TEDA-L33, manufactured by TOSOH CORPORATION)
.sup.8)N,N,N',N'-tetramethylhexamethylenediamine (TOYOCAT-MR,
manufactured by TOSOH CORPORATION)
.sup.9)N,N-dimethylcyclohexylamine (manufactured by Aldrich Co.)
.sup.10)Crude MDI (MR-200), manufactured by Nippon Polyurethane
K.K., INDEX = (mols of NCO groups/mols of OH groups) .times.
100
[0179] TABLE-US-00018 TABLE 18 Comparative Examples Examples 57 58
59 60 65 66 67 Reactivity (sec) Cream time 28 27 26 25 31 26 25 Gel
time 91 90 90 90 90 90 90 Tack free time 153 148 136 150 132 132
128 Rise time 159 157 150 158 148 146 143 Physical properties of
foam Flowability (cm) 79 78 77 78 70 72 72 Core density
(kg/m.sup.3) 30.4 30.5 30.5 30.8 31.9 30.5 30.6 Adhesive strength
1.66 1.72 1.81 1.43 0.94 1.07 1.01 (kgf/cm.sup.2) Dimensional
stability -1.1 -1.0 -0.9 -1.2 -2.2 -3.0 -3.2 (%)
[0180] As is evident from Table 18, it is possible to produce foams
excellent in flowability, adhesive strength and dimensional
stability by using amine compounds of the present invention as
catalysts.
[0181] Namely, Examples 57 to 60 are examples wherein rigid
polyurethane foams were produced by using the catalysts of the
present invention. In each Example, a rigid urethane foam excellent
in flowability, adhesive strength and dimensional stability, was
obtained.
[0182] Whereas, Comparative Examples 65 to 67 are examples wherein
tertiary amine catalysts having no alkyl ether group or no aryl
ether group in their molecules, were used, whereby the foams were
inferior in flowability, adhesive strength and dimensional
stability.
EXAMPLES 61 TO 64 AND COMPARATIVE EXAMPLES 68 TO 71
[0183] A polyol, a blowing agent and a foam stabilizer were mixed
in a blend ratio as identified in Table 19 to prepare Premix A.
47.1 g of Premix A was taken into a 300 ml polyethylene cup, and a
catalyst as identified in Table 19 was added in an amount such that
the reactivity as represented by the following gel time would be 90
seconds, whereupon the temperature was adjusted to 20.degree. C. A
polyisocyanate liquid (MR-200) having the temperature adjusted to
20.degree. C. in a separate container, was put into the cup of
Premix A in such an amount that the isocyanate index [isocyanate
groups/OH groups (molar ratio).times.100)] would be 110, and
immediately stirred by a stirrer at 6,500 rpm for 5 seconds. The
mixed and stirred liquid was transferred to a 2 liter polyethylene
cup having the temperature adjusted to 40.degree. C., and the
reactivity during foaming was measured. Then, the starting material
scale was increased, and in the same manner, the mixed liquid was
put into a mold having the temperature adjusted to 40.degree. C.,
whereupon foam molding was carried out. Upon expiration of 10
minutes from the introduction of the mixed liquid, the foam was
removed from the mold. From the molded foam, the flowability, core
density, adhesive strength and dimensional stability of the foam
were evaluated. The results are shown in Table 20. TABLE-US-00019
TABLE 19 Comparative Examples Examples 61 62 63 64 68 69 71 Blend
Premix A Polyol.sup.1) 100 100 100 100 100 100 100 (parts by
weight) HCFC-141b 11 11 11 11 11 11 11 Water 4.0 4.0 4.0 4.0 4.0
4.0 4.0 Foam stabilizer.sup.2) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Amine
catalyst Catalyst A.sup.3) 3.3 Catalyst B.sup.4) 3.7 Catalyst
C.sup.5) 1.8 Catalyst D.sup.6) 4.6 Catalyst E.sup.7) 1.6 Catalyst
F.sup.8) 1.2 Catalyst G.sup.9) 1.5 Isocyanate INDEX.sup.10) 110 110
110 110 110 110 110 .sup.1)Sucrose/aromatic amine type polyether
polyol (OH value = 440 mgKOH/g, manufactured by Asahi Glass
Company, Limited) .sup.2)Silicone type surfactant (tradename:
SZ-1627), manufactured by Nippon Unicar Co., Ltd.
.sup.3)N,N-dimethylaminoethyl methyl ether (Product obtained by
reacting N,N-dimethylaminoethanol with methyl iodide)
.sup.4)N,N-dimethylaminoethyl ethyl ether (Product obtained by
reacting N,N-dimethylaminoethanol with ethyl bromide)
.sup.5)N,N-dimethylaminohexyl methyl ether (Product obtained by
reacting N,N-dimethylaminohexanol with methyl iodide)
.sup.6)N-(2-methoxyethyl)-N'-methylpiperazine (Product obtained by
reacting N-(2-hydroxyethyl)-N'-methylpiperazine with methyl iodide)
.sup.7)Dipropylene glycol solution containing 33 wt % of
triethylenediamine (TEDA-L33, manufactured by TOSOH CORPORATION)
.sup.8)N,N,N',N'-tetramethylhexamethylenediamine (TOYOCAT-MR,
manufactured by TOSOH CORPORATION)
.sup.9)N,N-dimethylcyclohexylamine (manufactured by Aldrich Co.)
.sup.10) Crude MDI (MR-200), manufactured by Nippon Polyurethane
K.K., INDEX = (mols of NCO groups/mols of OH groups) .times.
100
[0184] TABLE-US-00020 TABLE 20 Comparative Examples Examples 61 62
63 64 68 69 71 Reactivity (sec) Cream time 25 24 22 23 29 24 25 Gel
time 91 90 90 90 90 90 90 Tack free time 156 151 148 152 146 147
143 Rise time 162 159 162 164 155 158 156 Physical properties of
foam Flowability (cm) 84 83 82 82 73 77 77 Core density
(kg/m.sup.3) 26.8 26.8 26.9 27.1 28.3 27.5 27.6 Adhesive strength
1.43 1.48 1.55 1.22 0.69 0.78 0.75 (kgf/cm.sup.2) Dimensional
stability -1.2 -1.1 -0.9 -1.4 -2.8 -4.5 -4.4 (%)
[0185] As is evident from Table 20, it is possible to produce foams
excellent in flowability, adhesive strength and dimensional
stability by using amine compounds of the present invention as
catalysts.
[0186] Namely, Examples 61 to 64 are examples wherein rigid
polyurethane foams were produced by using the catalysts of the
present invention. In each Example, a rigid urethane foam excellent
in flowability, adhesive strength and dimensional stability, was
obtained.
[0187] Whereas, Comparative Examples 68 to 71 are examples wherein
tertiary amine catalysts having no alkyl ether group or no aryl
ether group in their molecules, were used, whereby the foams were
inferior in flowability, adhesive strength and dimensional
stability.
[0188] Now, referring to Examples and Comparative Examples, the
catalyst for producing a rigid polyisocyanurate foam of the present
invention, and the process for producing a rigid polyisocyanurate
foam by using such a catalyst, will be described. However, it
should be understood that the present invention is by no means
restricted by such specific Examples.
[0189] Measured Items for the Reactivity
[0190] Cream time: The time until the foam starts to rise was
measured by visual observation.
[0191] Gel time: As the reaction proceeds, the time until the
liquid substance changes to a resinous substance, was measured.
[0192] Tack free time: The time until tackiness of the foam surface
disappears, was measured.
[0193] Rise time: The time until the rise of the foam stops, was
measured by visual observation.
[0194] Oxygen index: The oxygen index is an index to show the flame
retardancy of a foam, and the combustion test method was carried
out in accordance with ASTMD 2863D-74.
[0195] Core Density of Foam:
[0196] Free foaming was carried out in a 0.5L polyethylene cup, and
the center portion of the formed foam was cut into a size of
10.times.5.times.5 cm, whereupon the size and weight were
accurately measured, and the core density was calculated.
[0197] Adhesive Strength of Foam:
[0198] Free foaming was carried out by setting a zinc-lined iron
plate of 5.times.5 cm on the upper side of a 0.5 L polyethylene
cup. After foaming for 1 hour, the peel strength at 90.degree. of
the set iron plate was measured and taken as the adhesive strength
of the foam.
[0199] Dimensional Stability of Foam:
[0200] A foam freely foam in a 0.5 L polyethylene cup was
maintained under a condition of -30.degree. C..times.48 hours,
whereby a change in the thickness direction was measured.
EXAMPLES 65 TO 77 AND 90
[0201] A polyol, a blowing agent and a foam stabilizer were mixed
in a blend ratio as identified in Table 21 to prepare Premix A. As
the blowing agent, 1,1,1,3,3-pentafluoropropane (HFC-245fa) was
used. 24.0 g of Premix A was taken into a 0.5 L polyethylene cup,
and a catalyst as identified in Table 21 was added in an amount
such that the reactivity as represented by the following gel time
would be 12 to 13 seconds, whereupon the temperature was adjusted
to 10.degree. C. A polyisocyanate liquid (MR-200) having the
temperature adjusted to 10.degree. C. in a separate container, was
put into the cup of Premix A in such an amount that the isocyanate
index [isocyanate groups/OH groups (molar ratio).times.100)] would
be 210, and immediately stirred by a stirrer at 7,000 rpm for 3
seconds. The reactivity during foaming of the mixed and stirred
liquid, was measured. Then, using a foam freely foamed by the same
operation as described above, the oxygen index, core density,
adhesive strength and dimensional stability were evaluated.
EXAMPLES 78 TO 89
[0202] A polyol, a blowing agent and a foam stabilizer were mixed
in a blend ratio as identified in Table 21 to prepare Premix A. As
the blowing agent, 1,1,1,3,3-pentafluorobutane (HFC-365mfc) or
1,1-dichloro-l-fluoroethane (HCFC-141b) was used. 24.0 g of Premix
A was taken into a 0.5 L polyethylene cup, and a catalyst as
identified in Table 21 was added in an amount such that the
reactivity as represented by the following gel time would be 12 to
13 seconds, whereupon the temperature was adjusted to 20.degree. C.
A polyisocyanate liquid (MR-200) having the temperature adjusted to
20.degree. C. in a separate container, was put into the cup of
Premix A in such an amount that the isocyanate index [isocyanate
groups/OH groups (molar ratio).times.100)] would be 210, and
immediately stirred by a stirrer at 7,000 rpm for 3 seconds. The
reactivity during foaming of the mixed and stirred liquid, was
measured. Then, using a foam freely foamed by the same operation as
described above, the oxygen index, core density, adhesive strength
and dimensional stability were evaluated.
[0203] The results of Examples 65 to 90 are shown in Table 22
TABLE-US-00021 TABLE 21 Examples 65 66 67 68 69 70 71 Blend (parts
Premix A Polyol.sup.1) 40 40 40 40 40 40 40 by weight)
Polyol.sup.2) 40 40 40 40 40 40 40 Polyol.sup.3) 20 20 20 20 20 20
20 HFC - 245fa 28 28 28 28 28 28 28 HFC - 365mfc HCFC - 141b Flame
retardant.sup.4) 20 20 20 20 20 20 20 Water 3.0 3.0 3.0 3.0 3.0 3.0
3.0 Foam stabilizer.sup.5) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Organic acid
metal 0.2 0.2 0.2 0.2 0.2 0.2 0.2 salt catalyst.sup.6) Amine
Catalyst A.sup.7) 3.5 compound Catalyst B.sup.8) 4.4 Catalyst
C.sup.9) 5.5 Catalyst D.sup.10) 7.0 7.0 7.0 7.0 Polyiso-cyanurate
Catalyst E.sup.11) 22.0 22.0 catalyst Catalyst F.sup.12) 26.7 26.7
Catalyst G.sup.13) 7.0 Catalyst H.sup.14) 30.0 Catalyst I.sup.15)
12.0 Polyisocyanurate catalyst in the catalyst 86.3% 85.9% 68.6%
75.9% 79.2% 50.0% 81.1% composition (wt %) Isocyanate INDEX.sup.16)
210 210 210 210 210 210 210 Examples 72 73 74 75 76 77 Blend Premix
A Polyol.sup.1) 40 40 40 40 40 40 (parts by Polyol.sup.2) 40 40 40
40 40 40 weight) Polyol.sup.3) 20 20 20 20 20 20 HFC - 245fa 28 28
28 28 28 28 HFC - 365mfc HCFC - 141b Flame retardant.sup.4) 20 20
20 20 20 20 Water 3.0 3.0 3.0 3.0 3.0 3.0 Foam stabilizer.sup.5)
1.5 1.5 1.5 1.5 1.5 1.5 Organic acid metal salt catalyst.sup.6) 0.2
0.2 0.2 0.2 0.2 0.2 Amine Catalyst A.sup.7) compound Catalyst
B.sup.8) Catalyst C.sup.9) Catalyst D.sup.10) 2.0 3.4 6.5 9.3 16.0
26.0 Polyiso-cyanurate Catalyst E.sup.11) catalyst Catalyst
F.sup.12) Catalyst G.sup.13) Catalyst H.sup.14) Catalyst I.sup.15)
20.0 13.6 9.7 6.2 4.0 2.5 Polyisocyanurate catalyst in the catalyst
90.9% 80.0% 60.0% 40.0% 20.0% 8.8% composition (wt %) Isocyanate
INDEX.sup.16) 210 210 210 210 210 210 Examples 78 79 80 81 82 83 84
Blend (parts Premix A Polyol.sup.1) 40 40 40 40 40 40 40 by weight)
Polyol.sup.2) 40 40 40 40 40 40 40 Polyol.sup.3) 20 20 20 20 20 20
20 HFC - 245fa HFC - 365mfc 22 22 22 22 22 22 22 HCFC - 141b Flame
retardant.sup.4) 20 20 20 20 20 20 20 Water 3.0 3.0 3.0 3.0 3.0 3.0
3.0 Foam stabilizer.sup.5) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Organic acid
metal 0.2 0.2 0.2 0.2 0.2 0.2 0.2 salt catalyst.sup.6) Amine
Catalyst A.sup.7) 2.1 compound Catalyst B.sup.8) 2.6 Catalyst
C.sup.9) Catalyst D.sup.10) 4.2 4.2 4.2 4.2 4.2 Polyiso-cyanurate
Catalyst E.sup.11) 13.2 13.2 catalyst Catalyst F.sup.12) 16.0 16.0
Catalyst G.sup.13) 4.2 Catalyst H.sup.14) 18.0 Catalyst I.sup.15)
7.2 Polyisocyanurate catalyst in the catalyst 75.9% 79.2% 50.0%
81.1% 63.2% 86.3% 86.0% composition (wt %) Isocyanate INDEX.sup.16)
210 210 210 210 210 210 210 Examples 85 86 87 88 89 90 Blend Premix
A Polyol.sup.1) 40 40 40 40 40 40 (parts by Polyol.sup.2) 40 40 40
40 40 40 weight) Polyol.sup.3) 20 20 20 20 20 20 HFC - 245fa 28 HFC
- 365mfc 22 HCFC - 141b 26 26 26 26 Flame retardant.sup.4) 20 20 20
20 20 Water 3.0 1.5 1.5 1.5 1.5 3.0 Foam stabilizer.sup.5) 1.5 1.5
1.5 1.5 1.5 1.5 Organic acid metal salt catalyst.sup.6) 0.2 0.2 0.2
0.2 0.2 0.2 Amine Catalyst A.sup.7) 1.9 compound Catalyst B.sup.8)
2.3 Catalyst C.sup.9) 3.3 3.0 Catalyst D.sup.10) 3.8 7.0
Polyiso-cyanurate Catalyst E.sup.11) 11.9 catalyst Catalyst
F.sup.12) 14.4 Catalyst G.sup.13) Catalyst H.sup.14) Catalyst
I.sup.15) 7.2 6.5 6.5 12.0 Polyisocyanurate catalyst in the
catalyst 68.6% 86.2% 86.2% 68.4% 63.1% 63.2% composition (wt %)
Isocyanate INDEX.sup.16) 210 210 210 210 210 210 .sup.1)Waste PET
type polyester polyol (OH value = 241 mgKOH/g) manufactured by Oxid
L.P. .sup.2)Mannich type polyether polyol (OH value = 469 mgKOH/g)
manufactured by Daiichi Kogyo Seiyaku Co., Ltd. .sup.3)Aliphatic
amine type polyether polyol (OH value = 450 mgKOH/g), manufactured
by Asahi Glass Company, Limited. .sup.4)Trichloropropyl phosphate
(FYROL PCF, tradename), manufactured by AKZO NOBEL K.K.
.sup.5)Silicone type surfactant (tradename: L-5420), manufactured
by Nippon Unicar Co., Ltd. .sup.6)Lead 2-ethylhexylate (lead 20%
(T), manufactured by Nihon Kagaku Sangyo Co., Ltd.)
.sup.7)N,N-dimethylbutylamine (manufactured by Aldrich Co.)
.sup.8)N,N-dimethylhexylamine (manufactured by Aldrich Co.)
.sup.9)N,N-dimethyloctylamine (manufactured by Tokyo Kasei K.K.)
.sup.10)N,N-dimethyldodecylamine (manufactured by Tokyo Kasei K.K.)
.sup.11)Potassium 2-ethylhexanoate 75%, diethylene glycol 25%
(DABCO K15, manufactured by Air Products and Chemicals Inc.)
.sup.12)N-hydroxypropyl-N,N,N-trimethylammonium, 2-ethylhexanoate
75% and diethylene glycol 25% (DABCO TMR, manufactured by Air
Products and Chemicals Inc.)
.sup.13)1,3,5-Tris[3-(N,N-dimethylamino)propyl]hexahydro-1,3,5-triazine
(TOYOCAT-TRC, manufactured by TOSOH CORPORATION)
.sup.14)2,4,6-Tris(dimethylaminomethyl)phenol (manufactured by
Aldrich Co.) .sup.15)Methyltriethylammonium.2-ethylhexanoate
.sup.16)Crude MDI (MR-200), manufactured by Nippon Polyurethane
K.K., INDEX = (mols of NCO groups/mols of OH groups) .times.
100
[0204] TABLE-US-00022 TABLE 22 Examples 65 66 67 68 69 70 71 72 73
74 75 76 77 Reactivity (sec) Cream time 5 8 5 5 8 5 5 6 6 5 5 5 5
Gel time 13 13 12 13 13 13 13 12 12 12 12 12 12 Tack free time 18
18 21 18 18 22 18 21 21 21 21 21 21 Rise time 30 31 37 30 31 33 35
37 37 37 38 39 40 Physical properties of foam Oxygen Index (%) 28
28 28 28 28 28 28 28 28 28 28 28 27 Core density (kg/m.sup.3) 28.3
28.2 28.5 28.3 28.1 28.6 28.7 28.5 28.6 28.5 28.4 28.6 28.8
Adhesive strength 0.98 0.94 0.89 0.97 0.96 0.88 0.91 0.71 1.01 1.11
1.28 1.51 0.96 (kgf/cm.sup.2) Dimensional stability -0.6 -0.4 -0.1
-0.7 -0.6 -0.4 -0.6 -0.3 -0.2 -0.1 -0.1 -0.1 -0.4 (%) Examples 78
79 80 81 82 83 84 85 86 87 88 89 90 Reactivity (sec) Cream time 7 8
6 7 7 7 8 7 7 8 7 7 5 Gel time 12 12 12 12 12 12 12 12 12 12 12 12
12 Tack free time 21 21 22 21 22 21 22 21 21 21 20 22 21 Rise time
36 35 36 35 36 35 35 36 36 36 36 35 37 Physical properties of foam
Oxygen Index (%) 26 26 26 26 26 26 26 26 28 28 28 28 23 Core
density (kg/m.sup.3) 29.4 29.6 29.5 29.2 29.3 29.1 29.2 29.4 28.4
28.1 28.0 28.0 28.5 Adhesive strength 0.91 0.92 0.94 0.89 0.85 0.88
0.84 0.87 1.01 1.02 0.99 0.94 0.93 (kgf/cm.sup.2) Dimensional
stability -0.2 -0.1 -0.2 -0.1 -0.3 -0.4 -0.1 -0.2 -0.1 -0.1 -0.1
-0.1 -0.1 (%)
COMPARATIVE EXAMPLES 72 TO 79, 84 TO 85, 88 TO 89 AND 92
[0205] A polyol, a blowing agent and a foam stabilizer were mixed
in a blend ratio as identified in Table 23 to prepare Premix A. As
the blowing agent, 1,1,1,3,3-pentafluoropropane (HFC-245fa) was
used. 24.0 g of Premix A was taken into a 0.5 L polyethylene cup,
and a catalyst as identified in Table 23 was added in an amount
such that the reactivity as represented by the following gel time
would be 12 to 13 seconds, whereupon the temperature was adjusted
to 10.degree. C. A polyisocyanate liquid (MR-200) having the
temperature adjusted to 10.degree. C. in a separate container, was
put into the cup of Premix A in such an amount that the isocyanate
index [isocyanate groups/OH groups (molar ratio).times.100)] would
be 210, and immediately stirred by a stirrer at 7,000 rpm for 3
seconds. The reactivity during foaming of the mixed and stirred
liquid, was measured. Then, using a foam freely foamed by the same
operation as described above, the oxygen index, core density,
adhesive strength and dimensional stability were evaluated.
COMPARATIVE EXAMPLES 80 TO 83, 86 TO 87, 90 AND 91
[0206] A polyol, a blowing agent and a foam stabilizer were mixed
in a blend ratio as identified in Table 23 to prepare Premix A. As
the blowing agent, 1,1,1,3,3-pentafluorobutane (HFC-365mfc) or
1,1-dichloro-1-fluoroethane (HCFC-141b) was used. 24.0 g of Premix
A was taken into a 0.5 L polyethylene cup, and a catalyst as
identified in Table 23 was added in an amount such that the
reactivity as represented by the following gel time would be 12 to
13 seconds, whereupon the temperature was adjusted to 20.degree. C.
A polyisocyanate liquid (MR-200) having the temperature adjusted to
20.degree. C. in a separate container, was put into the cup of
Premix A in such an amount that the isocyanate index [isocyanate
groups/OH groups (molar ratio).times.100)] would be 210, and
immediately stirred by a stirrer at 7,000 rpm for 3 seconds. The
reactivity during foaming of the mixed and stirred liquid, was
measured. Then, using a foam freely foamed by the same operation as
described above, the oxygen index, core density, adhesive strength
and dimensional stability were evaluated.
[0207] The results of Comparative Examples 72 to 92 are shown in
Table 24. TABLE-US-00023 TABLE 23 Comparative Examples 72 73 74 75
76 77 78 79 80 81 82 Blend (parts Premix Polyol.sup.1) 40 40 40 40
40 40 40 40 40 40 40 by weight) AE Polyol.sup.2) 40 40 40 40 40 40
40 40 40 40 40 Polyol.sup.3) 20 20 20 20 20 20 20 20 20 20 20 HFC -
245fa 28 28 28 28 28 28 28 28 HFC - 365mfc 22 22 HCFC - 141b 26
Flame retardant.sup.4) 20 20 20 20 20 20 20 20 20 20 20 Water 3.0
3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 1.5 Foam stabilizer.sup.5) 1.5
1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Organic acid 0.2 0.2 0.2
0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 metal salt catalyst.sup.6) Amine
Catalyst A.sup.7) compound Catalyst B.sup.8) Catalyst C.sup.9)
Catalyst D.sup.10) Catalyst J.sup.11) 3.0 3.0 3.0 Catalyst
K.sup.12) 3.5 3.5 3.5 Catalyst L.sup.13) 4.4 4.4 Catalyst M.sup.14)
5.0 5.0 5.0 Polyiso- Catalyst E.sup.15) 22.0 22.0 22.0 cyanurate
Catalyst F.sup.16) 26.7 26.7 catalyst Catalyst G.sup.17) 7.0
Catalyst H.sup.18) 30.0 30.0 Catalyst I.sup.19) 12.0 12.0 12.0
Polyisocyanurate catalyst in 88.0% 89.9% 86.3% 88.4% 87.2% 73.2%
85.7% 70.6% 80.0% 81.5% 66.7% the catalyst composition (wt %)
Isocyanate INDEX.sup.20) 210 210 210 210 210 210 210 210 210 210
210 Comparative Examples 83 84 85 86 87 88 89 90 91 92 Blend (parts
by Premix Z Polyol.sup.1) 40 40 40 40 40 40 40 40 40 40 weight)
Polyol.sup.2) 40 40 40 40 40 40 40 40 40 40 Polyol.sup.3) 20 20 20
20 20 20 20 20 20 20 HFC - 245fa 28 28 28 28 28 HFC - 365mfc 22 22
HCFC - 141b 26 26 26 Flame retardant.sup.4) 20 20 20 20 20 20 20 20
20 Water 1.5 3.0 3.0 1.5 1.5 3.0 3.0 3.0 3.0 3.0 Foam
stabilizer.sup.5) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Organic
acid 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 metal salt
catalyst.sup.6) Amine compound Catalyst A.sup.7) 8.8 Catalyst
B.sup.8) 11.0 Catalyst C.sup.9) 13.8 Catalyst D.sup.10) 17.5
Catalyst J.sup.11) 3.0 Catalyst K.sup.12) Catalyst L.sup.13) 4.4
Catalyst M.sup.14) Polyiso- Catalyst E.sup.15) 33.0 cyanurate
Catalyst F.sup.16) 40.0 catalyst Catalyst G.sup.17) 7.0 Catalyst
H.sup.18) 45.0 Catalyst I.sup.19) 18.0 12.0 Polyisocyanurate
catalyst in 61.4% 0.0% 0.0% 0.0% 0.0% 100.0% 100.0% 100.0% 100.0%
80.0% the catalyst composition (wt %) Isocyanate INDEX.sup.20) 210
210 210 210 210 210 210 210 210 210 .sup.1)Waste PET type polyester
polyol (OH value = 241 mgKOH/g) manufactured by Oxid L.P.
.sup.2)Mannich type polyether polyol (OH value = 469 mgKOH/g)
manufactured by Daiichi Kogyo Seiyaku Co., Ltd. .sup.3)Aliphatic
amine type polyether polyol (OH value = 450 mgKOH/g), manufactured
by Asahi Glass Company, Limited. .sup.4)Trichloropropyl phosphate
(FYROL PCF, tradename), manufactured by AKZO NOBEL K.K.
.sup.5)Silicone type surfactant (tradename: L-5420), manufactured
by Nippon Unicar Co., Ltd. .sup.6)Lead 2-ethylhexylate (lead
20%(T), manufactured by Nihon Kagaku Sangyo Co., Ltd.)
.sup.7)N,N-dimethylbutylamine (manufactured by Aldrich Co.)
.sup.8)N,N-dimethylhexylamine (manufactured by Aldrich Co.)
.sup.9)N,N-dimethyloctylamine (manufactured by Tokyo Kasei K.K.)
.sup.10)N,N-dimethyldodecylamine (manufactured by Tokyo Kasei K.K.)
.sup.11)N,N-dimethylcyclohexylamine (manufactured by Aldrich Co.)
.sup.12)Dipropylene glycol solution containing 33 wt % of
triethylenediamine (TEDA-L33, manufactured by TOSOH CORPORATION)
.sup.13)N,N,N',N'-tetramethyl-1,6-hexanediamine (TOYOCAT-MR,
manufactured by TOSOH CORPORATION) .sup.14)N-methylmorpholine
(manufactured by Tokyo Kasei K.K.) .sup.15)potassium
2-ethylhexanoate 75%, diethylene glycol 25% (DABCO K15,
manufactured by Air Products and Chemicals Inc.)
.sup.16)N-hydroxypropyl-N,N,N-trimethylammonium, 2-ethylhexanoate
75% and diethylene glycol 25% (DABCO TMR, manufactured by Air
Products and Chemicals Inc.)
.sup.17)1,3,5-Tris[3-(N,N-dimethylamino)propyl]hexahydro-1,3,5-triazine
(TOYOCAT-TRC, manufactured by TOSOH CORPORATION)
.sup.18)2,4,6-Tris(dimethylaminomethyl)phenol (manufactured by
Aldrich Co.) .sup.19)Tetraalkyl type quaternary ammonium salt
catalyst (methyltriethylammonium.2-ethylhexanoate) .sup.20)Crude
MDI (MR-200), manufactured by Nippon Polyurethane K.K., INDEX =
(mols of NCO groups/mols of OH groups) .times. 100
[0208] TABLE-US-00024 TABLE 24 Comparative Examples 72 73 74 75 76
77 78 79 80 81 82 Reactivity (sec) Cream time 5 8 5 8 5 7 6 7 5 8 5
Gel time 13 13 13 13 12 12 12 12 12 12 13 Tack free time 18 18 18
18 21 21 22 21 21 21 22 Rise time 30 31 30 31 37 36 36 35 37 35 33
Physical properties of foam Oxygen Index (%) 26 26 26 26 26 26 26
26 24 24 26 Core density (kg/m.sup.3) 28.3 28.2 28.3 28.1 28.5 29.4
29.5 32.4 28.5 29.6 28.6 Adhesive strength (kgf/cm.sup.2) 0.49 0.47
0.49 0.48 0.49 0.44 0.47 0.33 0.44 0.46 0.44 Dimensional stability
(%) -1.2 -0.9 -1.4 -1.2 -0.7 -0.5 -0.5 -0.4 -0.4 -0.6 -0.9
Comparative Examples 83 84 85 86 87 88 89 90 91 92 Reactivity (sec)
Cream time 5 7 7 8 7 7 8 7 7 5 Gel time 13 12 12 12 12 12 12 12 12
12 Tack free time 18 22 21 22 21 21 21 20 22 21 Rise time 35 36 35
35 36 36 36 36 35 37 Physical properties of foam Oxygen Index (%)
26 21 21 21 21 26 26 25 25 22 Core density (kg/m.sup.3) 28.7 33.5
35.0 34.4 29.4 28.4 28.1 28.0 28.0 28.0 Adhesive strength
(kgf/cm.sup.2) 0.46 0.29 0.29 0.31 0.44 0.11 0.09 0.11 0.12 0.09
Dimensional stability (%) -0.9 -5.2 -6.6 -7.1 -6.4 -0.4 -0.4 -0.5
-0.6 -0.5
[0209] As is evident from Tables 22 and 24, it is possible to
produce foams excellent in flame retardancy, adhesive strength and
dimensional stability by using amine compounds of the present
invention as catalysts.
[0210] Namely, Examples 65 to 71 and 73 to 76 are examples wherein
rigid polyisocyanurate foams were produced by using the catalysts
of the present invention and 1,1,1,3,3-pentafluoropropane
(HFC-245fa) as a blowing agent. In each Example, a rigid
polyisocyanurate foam excellent in flame retardancy, adhesive
strength and dimensional stability, was obtained.
[0211] Further, Examples 78 to 89 are examples wherein rigid
polyisocyanurate foams were produced by using catalysts of the
present invention and 1,1,1,3,3-pentafluorobutane (HFC-365mfc) or
1,1-dichloro-1-fluoroethane (HCFC-141b) as a blowing agent. In each
Example, a rigid polyisocyanurate foam excellent in flame
retardancy, adhesive strength and dimensional stability was
obtained.
[0212] Examples 72 is an example wherein the composition of the
polyisocyanurate catalyst in the catalyst composition of the
present invention exceeded 90 wt %, whereby a slight decrease in
adhesive strength is observed. On the other hand, Example 77 is an
example wherein the composition of the polyisocyanurate catalyst in
the catalyst composition of the present invention was less than 10
wt %, a slight decrease in the flame retardancy and dimensional
stability of the foam is observed. Accordingly, it is evident that
the composition comprising from 10 to 90 wt % of an aliphatic amine
compound of the above formula (1) and from 90 to 10 wt % of the
polyisocyanurate catalyst, is advantageous from the viewpoint of
the cost.
[0213] Whereas, Comparative Examples 72 to 83 are examples wherein
rigid polyisocyanurate foams were produced by means of catalyst
compositions comprising an amine compound other than the aliphatic
amine compound of the present invention and the polyisocyanurate
catalyst, whereby the foams were inferior in the flame retardancy,
adhesive strength and dimensional stability.
[0214] Further, Comparative Examples 84 to 87 are examples wherein
rigid polyisocyanunate foams were produced by using only the
aliphatic amine compounds as catalysts, whereby large amounts of
the catalysts were required, and the foams were inferior in the
flame retardancy and dimensional stability. Further, Comparative
Examples 88 to 91 are examples wherein rigid polyisocyanurate foams
were produced by using only the polyisocyanurate catalyst
(trimerization catalyst) without using an aliphatic amine compound,
whereby the foams were inferior in the adhesive strength and
dimensional stability.
[0215] Example 90 and Comparative Example 92 are examples wherein a
rigid polyisocyanurate foam was produced without using a flame
retardant and using 1,1,1,3,3-pentafluoropropane (HFC-245fa) as a
blowing agent. In the case of Example 90 wherein the catalyst
composition of the present invention was used, a rigid
polyisocyanurate foam was obtained which was excellent in flame
retardancy, adhesive strength and dimensional stability as compared
with Comparative Example 92 wherein a catalyst composition
comprising an amine compound other than the amine compound of the
present invention and the polyisocyanurate catalyst, was used.
EXAMPLES 91 TO 100
[0216] A polyol, a blowing agent and a foam stabilizer were mixed
in a blend ratio as identified in Table 25 to prepare Premix A.
24.0 g of Premix A was taken into a 0.5 L polyethylene cup, and a
catalyst as identified in Table 25 was added in an amount such that
the reactivity as represented by the following gel time would be 29
to 30 seconds, whereupon the temperature was adjusted to 20.degree.
C. A polyisocyanate liquid (MR-200) having the temperature adjusted
to 20.degree. C. in a separate container, was put into the cup of
Premix A in such an amount that the isocyanate index [isocyanate
groups/OH groups (molar ratio).times.100)] would be 250, and
immediately stirred by a stirrer at 6,000 rpm for 5 seconds. The
reactivity during foaming of the mixed and stirred liquid, was
measured. Then, using a foam freely foamed by the same operation as
described above, the oxygen index, core density, adhesive strength
and dimensional stability were evaluated.
[0217] The results of Examples 91 to 100 are shown in Table 26.
TABLE-US-00025 TABLE 25 Examples 91 92 93 94 95 96 97 98 99 100
Blend (parts Premix A Polyol.sup.1) 80 80 80 80 80 80 80 80 80 80
by weight) Polyol.sup.2) 20 20 20 20 20 20 20 20 20 20 Cyclopentane
16 16 16 16 16 16 16 16 16 16 Flame retardant.sup.3) 20 20 20 20 20
20 20 20 20 20 water 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Foam
Stabilizer.sup.4) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Amine
Catalyst A.sup.5) 1.2 1.2 compound Catalyst B.sup.6) 1.3 1.3 1.3
Catalyst C.sup.7) 1.4 1.4 Catalyst D.sup.8) 1.6 1.6 1.6
Polyiso-cyanurate Catalyst E.sup.9) 4.5 4.5 catalyst Catalyst
F.sup.10) 5.4 5.4 Catalyst G.sup.11) 3.0 3.0 Catalyst H.sup.12) 4.5
4.5 Catalyst I.sup.13) 3.3 3.3 Polyisocyanurate catalyst in the
catalyst 78.9% 81.8% 69.8% 77.6% 71.7% 76.3% 79.4% 65.2% 73.8%
67.3% composition (wt %) Isocyanate INDEX.sup.14) 250 250 250 250
250 250 250 250 250 250 .sup.1)Waste PET type polyester polyol (OH
value = 241 mgKOH/g) manufactured by Oxid L.P. .sup.2)Mannich type
polyether polyol (OH value = 469 mgKOH/g) manufactured by Daiichi
Kogyo Seiyaku Co., Ltd. .sup.3)Trichloropropyl phosphate (FYROL
PCF, tradename), manufactured by AKZO NOBEL K.K. .sup.4)Silicone
type surfactant (tradename: L-5420), manufactured by Nippon Unicar
Co., Ltd. .sup.5)N,N-dimethylbutylamine (manufactured by Aldrich
Co.) .sup.6)N,N-dimethylhexylamine (manufactured by Aldrich Co.)
.sup.7)N,N-dimethyloctylamine (manufactured by Tokyo Kasei K.K.)
.sup.8)N,N-dimethyldodecylamine (manufactured by Tokyo Kasei K.K.)
.sup.9)Potassium 2-ethylhexanoate 75%, diethylene glycol 25% (DABCO
K15, manufactured by Air Products and Chemicals Inc.)
.sup.10)N-hydroxypropyl-N,N,N-trimethylammonium, 2-ethylhexanoate
75% and diethylene glycol 25% (DABCO TMR, manufactured by Air
Products and Chemicals Inc.)
.sup.11)1,3,5-Tris[3-(N,N-dimethylamino)propyl]hexahydro-1,3,5-triazine
(TOYOCAT-TRC, manufactured by TOSOH CORPORATION)
.sup.12)2,4,6-Tris(dimethylaminomethyl)phenol (manufactured by
Aldrich Co.) .sup.13)Tetraalkyl type quaternary ammonium salt
catalyst (methyltriethylammonium.2-ethylhexanoate) .sup.14)Crude
MDI (MR-200), manufactured by Nippon Polyurethane K.K., INDEX =
(mols of NCO groups/mols of OH groups) .times. 100
[0218] TABLE-US-00026 TABLE 26 Examples 91 92 93 94 95 96 97 98 99
100 Reactivity (sec) Cream time 13 14 8 9 9 13 14 8 9 9 Gel time 29
29 30 30 29 29 29 30 30 29 Tack free time 58 39 60 62 52 58 39 60
62 52 Rise time 86 76 77 74 85 86 76 77 74 85 Physical properties
of foam Oxygen Index (%) 26 26 26 26 26 26 26 26 26 26 Core density
(kg/m.sup.3) 29.2 30.5 30.7 31.0 30.4 29.2 30.5 30.7 31.0 30.4
Adhesive strength (kgf/cm.sup.2) 0.35 0.29 0.32 0.31 0.38 0.35 0.29
0.32 0.31 0.38 Dimensional stability (%) -0.2 -0.1 -0.2 -0.1 -0.2
-0.2 -0.1 -0.2 -0.1 -0.2
COMPARATIVE EXAMPLES 93 to 103
[0219] A polyol, a blowing agent and a foam stabilizer were mixed
in a blend ratio as identified in Table 27 to prepare Premix A.
24.0 g of Premix A was taken into a 0.5 L polyethylene cup, and a
catalyst as identified in Table 27 was added in an amount such that
the reactivity as represented by the following gel time would be 29
to 30 seconds, whereupon the temperature was adjusted to 20.degree.
C. A polyisocyanate liquid (MR-200) having the temperature adjusted
to 20.degree. C. in a separate container, was put into the cup of
Premix A in such an amount that the isocyanate index [isocyanate
groups/OH groups (molar ratio).times.100)] would be 250, and
immediately stirred by a stirrer at 6,000 rpm for 5 seconds. The
reactivity during foaming of the mixed and stirred liquid, was
measured. Then, using a foam freely foamed by the same operation as
described above, the oxygen index, core density, adhesive strength
and dimensional stability were evaluated.
[0220] The results of Comparative Examples 93 to 103 are shown in
Table 28. TABLE-US-00027 TABLE 27 Comparative Examples 93 94 95 96
97 98 99 100 101 102 103 Blend (parts Premix A Polyol.sup.1) 80 80
80 80 80 80 80 80 80 80 80 by weight) Polyol.sup.2) 20 20 20 20 20
20 20 20 20 20 20 Cyclopentane 16 16 16 16 16 16 16 16 16 16 16
Flame retardant.sup.3) 20 20 20 20 20 20 20 20 20 20 20 Water 1.5
1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Foam stabilizer.sup.4) 1.5
1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Amine Catalyst A.sup.5)
compound Catalyst B.sup.6) 3.3 Catalyst C.sup.7) Catalyst D.sup.8)
4.0 Catalyst J.sup.9) 1.4 1.4 Catalyst K.sup.10) 1.2 1.2 Catalyst
L.sup.11) 1.0 1.0 Catalyst M.sup.12) Polyiso- Catalyst E.sup.13)
4.5 4.5 4.5 cyanurate Catalyst F.sup.14) 5.4 13.5 catalyst Catalyst
G.sup.15) 7.5 Catalyst H.sup.16) Catalyst I.sup.17) 3.3 3.3 8.3
Polyisocyanurate catalyst 76.3% 79.4% 78.9% 73.3% 81.8% 76.7% 0.0%
0.0% 100.0% 100.0% 100.0% in the catalyst composition (wt %)
Isocyanate INDEX.sup.18) 250 250 250 250 250 250 250 250 250 250
250 .sup.1)Waste PET type polyester polyol (OH value = 241 mgKOH/g)
manufactured by Oxid L.P. .sup.2)Mannich type polyether polyol (OH
value = 469 mgKOH/g) manufactured by Daiichi Kogyo Seiyaku Co.,
Ltd. .sup.3)Trichloropropyl phosphate (FYROL PCF, tradename),
manufactured by AKZO NOBEL K.K. .sup.4)Silicone type surfactant
(tradename: L-5420), manufactured by Nippon Unicar Co., Ltd.
.sup.5)N,N-dimethylbutylamine (manufactured by Aldrich Co.)
.sup.6)N,N-dimethylhexylamine (manufactured by Aldrich Co.)
.sup.7)N,N-dimethyloctylamine (manufactured by Tokyo Kasei K.K.)
.sup.8)N,N-dimethyldodecylamine (manufactured by Tokyo Kasei K.K.)
.sup.9)N,N-dimethylcyclohexylamine (manufactured by Aldrich Co.)
.sup.10)Dipropylene glycol solution containing 33 wt % of
triethylenediamine (TEDA-L33, manufactured by TOSOH CORPORATION)
.sup.11)N,N,N',N'-tetramethyl-1,6-hexanediamine (TOYOCAT-MR,
manufactured by TOSOH CORPORATION) .sup.12)N-methylmorpholine
(manufactured by Tokyo Kasei K.K.) .sup.13)Potassium
2-ethylhexanoate 75%, diethylene glycol 25% (DABCO K15,
manufactured by Air Products and Chemicals Inc.)
.sup.14)N-hydroxypropyl-N,N,N-trimethylammonium, 2-ethylhexanoate
75% and diethylene glycol 25% (DABCO TMR, manufactured by Air
Products and Chemicals Inc.)
.sup.15)1,3,5-Tris[3-(N,N-dimethylamino)propyl]hexahydro-1,3,5-triazine
(TOYOCAT-TRC, manufactured by TOSOH CORPORATION)
.sup.16)2,4,6-Tris(dimethylaminomethyl)phenol (manufactured by
Aldrich Co.) .sup.17)Tetraalkyl type quaternary ammonium salt
catalyst (methyltriethylammonium.2-ethylhexanoate) .sup.18)Crude
MDI (MR-200), manufactured by Nippon Polyurethane K.K., INDEX =
(mols of NCO groups/mols of OH groups) .times. 100
[0221] TABLE-US-00028 TABLE 28 Comparative Examples 93 94 95 96 97
98 99 100 101 102 103 Reactivity (sec) Cream time 13 14 13 9 13 9 8
9 14 15 13 Gel time 29 29 29 29 29 29 30 29 29 30 29 Tack free time
58 39 58 52 58 52 60 58 39 60 52 Rise time 86 76 86 85 86 85 77 86
76 77 85 Physical properties of foam Oxygen Index (%) 24 24 24 24
24 24 21 21 24 24 24 Core density (kg/m.sup.3) 29.2 30.5 29.2 30.4
29.2 30.4 35.7 35.5 30.5 30.7 30.4 Adhesive strength 0.11 0.12 0.1
0.08 0.11 0.09 0.08 0.08 0.02 0.01 0.12 (kgf/cm.sup.2) Dimensional
stability -0.8 -1.1 -1.4 -0.9 -1.1 -1.2 -7.5 -8.8 -1.2 -1.3 -1.2
(%)
[0222] As is evident from Tables 26 and 28, it is possible to
produce foams excellent in flame retardancy, adhesive strength and
dimensional stability by using amine compounds of the present
invention as catalysts.
[0223] Namely, Examples 91 to 100 are examples wherein rigid
polyisocyanurate foams were produced by using the catalysts of the
present invention and cyclopentane as a blowing agent. In each
Example, a rigid polyisocyanurate foam excellent in flame
retardancy, adhesive strength and dimensional stability, was
obtained.
[0224] Whereas, Comparative Examples 93 to 98 are examples wherein
rigid polyisocyanurate foams were produced by using a catalyst
composition comprising an amine compound other than the amine
compound of the present invention and the polyisocyanurate
catalyst, whereby the foams were inferior in flame retardancy,
adhesive strength and dimensional stability.
[0225] Further, Comparative Examples 99 and 100 are examples
wherein rigid polyisocyanurate foams were produced by using only
aliphatic amine compounds as catalysts, whereby large amounts of
the catalysts were required, and the foams were inferior in flame
retardancy, adhesive strength and dimensional stability. Further,
Comparative Examples 101 to 103 are examples wherein rigid
polyisocyanurate foams were produced by using only the
polyisocyanurate catalyst as the catalyst without using an amine
compound of the present invention, whereby the foams were inferior
in adhesive strength and dimensional stability.
[0226] The entire disclosures of Japanese Patent Application No.
2002-205506 filed on Jul. 15, 2002, Japanese Patent Application No.
2002-245644 filed on Aug. 26, 2002, Japanese Patent Application No.
2002-261282 filed on Sep. 6, 2002 and Japanese Patent Application
No. 2003-110020 filed on Apr. 15, 2003 including specifications,
claims and summaries are incorporated herein by reference in their
entireties.
* * * * *